Advances on secondary lithium ion batteries imply the use of solid polymer electrolytes, which represent a promising solution to improve safety issues in high energy density batteries. Through dissolution of lithium salts into a polymeric host, such as poly(ethylene oxide) (PEO), ion conducting polymers are obtained. The Li+ ions will be localized in the proximity of the oxygen atoms in the PEO chains and thus, their motion strongly correlated with the segmental reorientation of the polymer. Nuclear magnetic resonance (NMR) spectroscopy, translational diffusion coefficients and transverse relaxation times (T2) contribute to the understanding of the involved structures and the ongoing dynamical processes in ionic conductivity. Nuclei with different motional freedom can present different T2 times. T2xT2 exchange experiments enable studying exchange processes between nuclei from different motional regimes. In this work, three different ion conducting polymers were studied. First, PEG was doped with different amounts of LiClO4. 7Li NMR relaxometry measurements were done to study dynamical behavior of the lithium ions in the amorphous phase. All samples presented two lithium types with clearly differentiated T2 times, indicating the presence of two regions with different dynamics. The mobility and consequently the T2 times, increases with temperature. It was observed, that the doping ratio strongly influences the dynamics of the lithium ions, as the amount of crystalline PEG is reduced while increasing the polarity of the sample. A local maximum of the mobility was observed for y = 8. With the T2xT2 exchange experiments exchange rates between both lithium sites were quantified. Second, the triblock copolymer PS-PEO-PS doped with LiTFSI was studied with high resolution solid state NMR techniques as well as with 7Li relaxometry measurements. T1ρ and spin diffusion measurements gave insight on the influence of the doping and the PS/PEO ratio on the mobility of the different segments and on interdomain distances of the lamellar phases. Third, multiple quantum diffusion measurements were applied on poly(ethylene glycol) distearate (PEGD) doped with LiClO4. Therefore, triple quantum states of the 3/2 nucleus 7Li were excited. After optimizing the experimental procedure, it was possible to obtain reliable diffusion coefficients using triple quantum states. / O avanço da tecnologia em baterias secundárias de íons lítio envolve o uso de polímeros condutores iônicos como eletrólitos, os quais representam uma solução promissora para obter baterias de maior densidade de energia e segurança. Polímeros condutores são formados através da dissolução de sais de lítio em uma matriz polimérica, como o poli(óxido de etileno) (PEO). Os íons de lítio estão localizados próximos aos oxigênios do PEO, de tal forma que seu movimento está correlacionado com a reorientação das cadeias poliméricas. Espectroscopia por Ressonância magnética nuclear (RMN), junto com medidas de difusão translacional e tempos de relaxação transversal (T2) contribuem para elucidar as estruturas e os processos dinâmicos envolvidos na condutividade iônica. Núcleos com diferente liberdade de movimentação podem ter tempos de T2 diferentes. Experimentos de T2xT2 permitem correlacionar sítios de diferentes propriedades dinâmicas. Neste trabalho, três diferentes polímeros condutores iônicos foram estudados. Primeiro, PEG foi dopado com LiClO4. As propriedades dinâmicas dos íons lítio na fase amorfa foram estudadas com medidas de relaxometria por RMN do núcleo 7Li. Todas as razões de dopagem apresentaram dois T2 diferentes, indicando dos tipos de lítio com dinâmica diferente. A mobilidade, e consequentemente os tempos T2 aumentam com aumento da temperatura. Foi identificado que a dopagem fortemente influencia a dinâmica dos íons lítio, devido à redução da fase cristalina PEG e o aumento da polaridade na amostra. Um máximo local da mobilidade foi observado para y = 8. Com o experimento T2xT2 foram quantificadas as rações de troca entre os dois tipos de lítio. Segundo, o copolímero tribloco PS-PEO-PS dopado com LiTFSI foi analisado através de técnicas de RMN de estado sólido de alta resolução assim como através de medidas de relaxação de 7Li. Medidas de T1ρ e difusão de spin mostraram a influência da dopagem e da razão PS/PEO na mobilidade dos diferentes segmentos e nas distâncias interdomínio das fases lamelares. Terceiro, medidas de difusão através de estados de múltiplos quanta foram feitas em diesterato de polietileno glicol (PEGD) dopado com LiClO4. Estados de triplo quantum foram criados no núcleo 7Li, spin 3/2. Após garantir a eficiência das ferramentas desenvolvidas, foi possível obter coeficientes de difusão confiáveis.

Esse trabalho descreve a caracterização térmica, estrutural e elétrica do sistema vítreo 50B203-(50-x)PbO-xLiF com x variando de 0,0 a 50,0. A técnica de calorimetria diferencial exploratória (DSC) foi utilizada na determinação das temperaturas características. A difratometria de raios x foi utilizada na detecção e identificação de fases cristalinas originadas durante a síntese ou durante o processo de aquecimento das amostras. As técnicas de espectroscopia Raman e Ressonância Magnética Nuclear (RMN) foram utilizadas na obtenção de informações estruturais da ordem a curto alcance em função da composição das amostras. A técnica de espectroscopia de impedância complexa foi utilizada na determinação das condutividades elétrica em função da quantidade de LiF e da temperatura. Amostras vítreas sem a presença de fases cristalinas foram obtidas para composições contendo no máximo 40moI % de LiF. Através da análise da medida de densidade, foi possível constatar que o aumento da quantidade de LiF leva a formação de uma estrutura mais aberta. A análise do espectro Raman das amostras vítreas mostrou que com o aumento da concentração de LiF, ocorre uma mudança significativa nas unidades estruturais borato presentes nas amostras. Na amostra vítrea contendo 40 mol% de LiF observou-se a existência de uma superunidade estrutural formada por diferentes unidades borato. Apesar dessa variação das unidades borato, as medidas de RMN do 11B mostraram que a razão entre as unidades trigonal B03 e tetraédrica B04 permanece praticamente constante em todo intervalo de composição analisada. A condutividade elétrica aumenta à medida que a concentração de LiF aumenta devido ao aumento do numero de portadores de carga. A 330°C uma condutividade de 3,55 x 10-5 S/cm foi medida para a amostra contendo 40 moI % de LiF. Utilizando as amostras contendo 40 e 45 mol% de LiF preparadas e caracterizadas durante a realização desse trabalho, foi possível construir um dispositivo para ser utilizado na demonstração do processo de condução elétrica em materiais vítreos condutores para alunos do ensino médio / This work describes the thermal, structural and electric characterization of 50B203-(50-x)PbO-xLiF glass system with x varying from 0,0 to 50,0. The differential scanning calorimetry (DSC) technique was used to determine the glass transition and the crystallization temperatures. The X-ray diffraction technique was used to detect and in the identification of the crystallized phases present on the glassy samples after the melt and during the heating. The Raman spectroscopy and the Nuclear Magnetic Resonance techniques were used in order to verify the structural changes induced by the substitution of PbO by LiF on the anionic borate units and on the B03/B04 species ratio. The impedance complex spectroscopy technique was used to evaluate the variation of the electrical conductivity and activation energy as a function of the LiF content. Homogenous glassy sample containing less than 45 mol % of LiF without any trace of crystallization were obtained. The analysis of the Raman spectra shows that as the amount of LiF increases the concentration of anionic borate species changes and that these changes are an indicative of the formation of B-F bonds. However, according to the 11B NMR data, these structural rearrangement should be of such nature that the ratio sup>[3]B/[4]B is near1y invariant. As expected, the electrical conduction increases as the amount of LiF increases because the number of carriers increases. At 330°C; , the conductivity varies from 3.93 x 10-10 (S/cm) for the sample without LiF to 3.55 x 10-5(S/cm) for the sample containing 40 mol % of LiF. The activation energy (Ea) varied respectively from 1.55 eV to 0.97 eV. Using the glassy samples with 40 and 45 mol% of LiF, we could built a set up that can be used to demonstrate the electrical conduction process on glass materials to high school students

O objetivo deste trabalho consiste na caracterização do polímero PolyParaPhenylene (PPP) dopado com FeCl3, usando a técnica de Espectroscopia de Alta Resolução em Sólidos por Ressonância Magnética Nuclear. Os espectros de alta resolução de 13C foram obtidos usando, simultaneamente, as técnicas de desacoplamento em alta potencia (DEC) e rotação da amostra em torno do angulo mágico (MASS). Alterações nos espectros de 13C do PPP dopado com FeCl3 causadas por defeitos na cadeia polimérica, tal como polarons e bipolarons, foram analisadas. Efeitos de variação de temperatura e purificação sobre os espectros do PPP, também foram estudados. As amostras foram, adicionalmente, caracterizadas por outras técnicas espectroscópicas, tal como Ressonância Paramagnética Eletrônica (EPR), Efeito Mossbauer, Infra Vermelho e Absorção Atômica; bem como por medidas de Condutividade. Nos observamos que as alterações nas larguras de linha de RMN, estão relacionadas com o aparecimento de bipolarons na cadeia polimérica. / The objective of this work consist of the characterization of FeCl3 doped PolyParaPhenylene (PPP) polymer, using Solid State High Resolution Nuclear Magnetic Resonance Spectroscopy. The 13C high resolution spectra were obtained simultaneously using High Power Decoupling (DEC) and Magic Angle Sample Spinning (MASS) techniques. Alterations in the high resolution 13C spectra of FeCl3 doped PPP caused by defects in the polymer chain such as polarons and bipolarons were analyzed. Effect of temperature variation and purification upon the PPP spectra was also studied. The samples were additionally characterized by others spectroscopic techniques such as Electron Paramagnetic Resonance (EPR), Mossbauer Effect, Infrared and Atomic Absorption as well as by conductivity measurements. We observed that the NMR linewidth changes are related to appearance of the bipolaron in the polymeric chain

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-10-10T12:18:35Z No. of bitstreams: 1 brunanadianevesdasilva.pdf: 7267349 bytes, checksum: 105653b8c907fb40f7e88e2da5b3173c (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-10-10T12:23:12Z (GMT) No. of bitstreams: 1 brunanadianevesdasilva.pdf: 7267349 bytes, checksum: 105653b8c907fb40f7e88e2da5b3173c (MD5) / Made available in DSpace on 2017-10-10T12:23:12Z (GMT). No. of bitstreams: 1 brunanadianevesdasilva.pdf: 7267349 bytes, checksum: 105653b8c907fb40f7e88e2da5b3173c (MD5) Previous issue date: 2017-07-28 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nióbio está entre os metais de alta importância tecnológica e o Brasil tem a maior reserva, produção global e do comércio nessa área. As perovskitas (ABO3), tais como o PZT, exibem propriedades ferroelétricas e piezoelétricas, importantes no setor eletrônico. Por questões ambientais busca-se por materiais livres de chumbo e o niobato de sódio (NaNbO3) é um bom candidato nesse caso, pois também possui uma série de fases em função da temperatura. Porém, esse polimorfismo ainda é pouco compreendido experimentalmente e cálculos DFT podem ser uma boa ferramenta de auxílio para estudo estrutural. Portanto, foi dado como objetivo do trabalho investigar fases do NaNbO3, comparando resultados teóricos e experimentais. O NaNbO3 foi sintetizado pelo Nb2O5 e tratado termicamente para caracterizações por TG-DTA, RMNES de 23Na e DRX. Modelos teóricos foram elucidados a partir de dados da literatura e todos os cálculos ab initio usando DFT se procederam com o pacote de programa QUANTUM ESPRESSO. As otimizações de geometria tiveram boa concordância com os parâmetros da literatura. A análise térmica confirmou formação do niobato. Após tratamento térmico, foram comparados picos de difrações de raios X das amostras com as simulações dos modelos otimizados. As análises de RMNES do núcleo de 23Na mostrou distinção entre os sítios químicos nas amostras pela convolução de sinais quadrupolares obtidos no cálculo, servindo, portanto, como uma sonda para o estudo desse polimorfismo. Além disso, os parâmetros de RMNES calculados dos núcleos de 93Nb identificou as distorções estruturais de cada fase. Ambas as técnicas concluíram que as amostras B1 e C1 sugeriram ser da fase S; D2 entre a R e a S; D1 entre as fases P e R. Pela estrutura de bandas, houve decaimento de gap para a sequência das fases. Cálculos de pDOS e cargas de Bader indicaram que essas propriedades eletrônicas não foram alteradas pelas diferenças estruturais entre os modelos. O cálculo de fônons identificou uma frequência imaginária na fase cúbica e foi proposto modificações dentro da célula unitária. Os espectros de IV das fases mostraram acoplamentos específicos de modos vibracionais, cuja diferenças entre elas se deve às distorções estruturais. A análise termodinâmica concluiu que a fase B possuía o maior valor de energia total, porém, pelas variações energéticas de menos de 2 kcal/mol, não havia como predizer pela DFT qual delas era a mais estável. / Niobium is among the metals for high technological importance and Brazil has the largest reserve, global production and trade in this area. The perovskites (ABO3), such as PZT, exhibits ferroelectric and piezoelectric properties, important to electronic setor. For environmental reasons, lead-free ceramics are used and sodium niobate (NaNbO3) is good candidate in this case, which also has a series of phases as a function of temperature. However, this polymorphism is still little known experimentally and DFT calculations can be a good tool for the structural study. Therefore, the goal of this work was to investigate phases of the NaNbO3, comparing theoretical and experimental results. Sodium niobate was synthesized by Nb2O5, and thermally treated for their characterizations by TG-DTA, solid-state NMR 23Na nuclei and Xray diffraction. Theoretical models were building from literature datas and all the ab initio calculations using DFT were done with program package QUANTUM ESPRESSO. The geometry’s optimizations had good agreement with the parameters of literature. The thermal analysis confirmed the formation of the niobate. After thermal treatment, the peaks of X-ray diffraction were compared with the simulations of the optimized models. The solidstate NMR analysis of the 23Na nuclei showed distinction between chemical sites at the samples according to the convolution of quadrupole signals obtained by calculations, thus serving as a probe for identification of polymorphism. In addition, the NMR parameters calculated of 93Nb nuclei identified the structural distortions of each phases. The both techniques concluded that the B1 and C1 samples suggested to be of S phase; D2 was between R and S; D1 was an intermediate of the P and R phases. By the band’s structure, there was a decreasing of gap for the sequence of phases. Bader charge analysis and pDOS calculations indicated that these electronic properties were not altered by structural differences between the models. The phonon calculations identified an imaginary frequency in the cubic phase and modifications was proposed inside the unit cell. The IR spectra of the phases showed specified couplings of vibrational modes, whose the differences between them are due to structural distortions. The thermodynamic analysis conclude that B phase had the highest total energy value, however, by the variations of energy less than 2 kcal.mol-1 there was no way to predict by DFT which one was the most stable.

Orientador: Anita Jocelyne Marsaioli / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T07:45:46Z (GMT). No. of bitstreams: 1 Martins_LucasGelain_D.pdf: 5948717 bytes, checksum: d64f37183bfefec1cedc88b263d32340 (MD5) Previous issue date: 2014 / Resumo: Nesta tese consiste no estudo de interações supramoleculares utilizando diferentes metodologias de Ressonância Magnética Nuclear de hidrogênio (RMN de 1H), tais como ROESY 1D, RMN-DOSY e RMN-STD. Os sistemas supramoleculares foram abordados em dois casos de estudo diferentes. O Capítulo I tem como objeto de estudo interações do fármaco Dapsona com diferentes carreadores de fármacos (ß-CD, SBE-ß-CD e lipossoma de EPC), com a finalidade de encontrar formulações nas quais a Dapsona seja mais solúvel. Os complexos binários e ternário formados foram determinadas por medidas de difusão molecular. Foram observadas as formações dos complexos Dap/ß-CD, Da-/SBE-ß-CD, Dap/EPC e o ternário Dap/ß-CD/EPC, os quais contribuem para o aumento de solubilidade do fármaco. O objeto de estudo apresentado no Capítulo II é a inibição da enzima acetilcolinesterase por dois alcaloides, a Fisostigmina e a Crinina. Para determinação das constantes de dissociação aparentes foram utilizados os crescimentos iniciais das curvas de saturação obtids por RMN-STD para construção das Isotermas de Langmuir. De acordo com os valores de constantes obtidos foi possível concluir que a AchE tem mais afinidade com a Fisostigmina do que com a Crinina / Abstract: This thesis consists of the supramolecular interactions study applying different Nuclear Magnetic Resonance methodologies (1H NMR) such as 1D ROESY, DOSY-NMR and STD-NMR. The supramolecular systems were addressed in two different case studies. In chapter I Dapsone solubility was the case study. To solve the solubility problem the interactions between Dapsone and various drug carriers (ß-CD , SBE-ß-CD and EPC liposome) were characterized in terms of the binary and ternary complexes structure using NMR method, such as 1D ROESY and STD-NMR and apparent association constants were determined by measuring molecular diffusion using DOSY-NMR. Dap/ß-CD, Dap/SBE-ß-CD, Dap/EPC and Dap/ß-CD/EPC complexes were observed and Dapsone water solubility was increased. The case study in Chapter II is the inhibition of acetylcholinesterase by two alkaloids, Physostigmine and Crinina. The apparent dissociation constants were determined using the initial growth saturation curves obtained by STD-NMRto construct the Langmuir isotherms. The constants showed that the AChE has more affinity for the Physostigmine than Crinine / Doutorado / Quimica Organica / Doutor em Quimica

Vibrio cholerae acquiert les gènes de la toxine cholérique suite à l’infection par le phage CTXphi et devient par la suite une bactérie pathogène. L'infection se déroule en deux étapes : une interaction entre le pilus TCP et le domaine pIIIN2ctx, puis la formation du complexe TolAIIIV.c/pIIIN1ctx. Cette seconde étape est l’étape limitante de l’infection. L’objectif général de ma thèse a été d’étudier les forces motrices associées à cette étape.1) J’ai étudié les mécanismes moléculaires associés à la spécificité phage/bactérie en ciblant les interactions électrostatiques et le feuillet intermoléculaire par RMN et double hybride bactérien.2) J’ai résolu la structure de TolAIIIV.c libre par RMN. La comparaison des structures de cette protéine à l’état libre et liée ont permis de mettre en évidence un changement conformationnel et de proposer un mécanisme moléculaire d’ajustement induit. De plus, l’étude de la flexibilité de la protéine par RMN à haute pression (HP) a montré l’importance de la cavité interne de la protéine TolAIII pour favoriser l’ajustement induit lors de la formation du complexe TolAIIIV.c/pIIIN1CTX.3) J’ai vérifié si l’ajustement induit observé précédemment était lié à la présence de cette cavité d’une manière générale chez les protéines TolAIII. Une étude de dispersion de relaxation et de RMN à HP de la protéine TolAIIIE.c a permis de vérifier l’importance de cette cavité pour le mécanisme d’ajustement induit essentiel à cette famille de protéine. De plus, nous avons corrélée la flexibilité particulière de la protéine TolAIIIE.c à la présence d’une boucle qui lui confère une certaines flexibilité nécessaires pour interagir avec plusieurs partenaires. / Vibrio cholerae becomes a pathogen after CTXphi phage infection. The phagic infection is a wo step mechanism: first TCP pilus binds to pIIIN2ctx, then TolAIIIV.c binds to pIIIN1ctx. The second step is essential for the acquisition of genes of cholera toxins leading to cholera disease. The main goal of my thesis is to study the driving forces associated to the phage infection.First, I studied the molecular mechanism associated to phage/bacteria specificity targeting electrostatic bonds and hydrophobic interactions within the intermolecular sheet. These experiments use NMR and bacterial two hybrids methods. Our results show that electrostatic bonds are essential for the complex formation.Second, I solved the solution structure of TolAIIIV.c using NMR. The comparison of the structures of free and bound states of TolAIIIV.c, shows an associate conformational change and lead us to propose a model for the molecular mechanism of the induced fit. Then the study of the TolAIII flexibility, using high pressure NMR shows the importance of TolAIII cavity to promote the induced fit during TolAIIIV.c/pIIIN1ctx complex formation.Finally, we wanted to show if the induced fit is correlated to the presence of cavity in TolAIII family. A study using NMR relaxation dispersion and high-pressure NMR experiments on TolAIIIE.c shows the importance of this cavity for the induced fit. The presence of a loop at the top of the N-terminal helix in TolAIIIE.c leads to the protein to have several conformations necessary to interact with many partners.

Ce travail de thèse s'intéresse à la structure de verres d'oxydes simples, riches en bore et en terre rare (TR). Cette famille de verres trouve des applications dans différents domaines, de l'optique au confinement des déchets nucléaires. Ici, nous étudions la structure de verres du système le plus simple regroupant ces deux oxydes, à savoir le binaire B2O3-TR2O3. Un intérêt particulier est porté à la composition métaborate de terre rare TRB3O6, à fusion congruente. Cette étude structurale est menée au moyen de différentes techniques spectroscopiques, notamment la RMN du solide sur les noyaux 11B et 17O, l'absorption optique de Nd3+ et la diffusion des neutrons et des rayons X, associée à de la modélisation par RMC. Nous obtenons ainsi des informations sur la structure du réseau vitreux (nature des groupements structuraux, connectivité du réseau¿) et l'environnement des ions TR3+. La tendance à la cristallisation de ces verres binaires est également étudiée, par ATD, DRX et MEB. Le second volet de ces travaux concerne le système ternaire SiO2-B2O3-TR2O3. Tout d'abord, l'étendue du domaine vitrifiable est déterminée, pour nos conditions d'élaboration, puis certains verres homogènes et transparents obtenus font l'objet d'une étude structurale, de manière analogue aux verres du système binaire. Les premiers résultats concernant la tendance à la cristallisation de ces verres sont obtenus. / This work focuses on the structure of boron and rare earth (RE) rich simple oxide glasses. This family of glasses finds applications in various fields, from optical materials to nuclear waste storage. Here, we study the glass structure of the simplest system combining these two oxides, namely the binary system B2O3-RE2O3. Particular attention is paid to the rare earth metaborate composition REB3O6, which exhibits a congruent melting. This structural study combines different spectroscopic techniques, such as solid state NMR on 17O and 11B nuclei, optical absorption (Nd3+) and neutron and X-rays scattering, coupled with RMC simulation. Information concerning the glassy network (nature of the structural units, network connectivity…) and the rare earth environment is gathered. The tendency towards crystallization of these binary glasses is also studied, using DTA, XRD and SEM. The second part of this work deals with the ternary system SiO2-B2O3-TR2O3. First, the extension of the domain where homogeneous and transparent glasses can be obtained (in our experimental conditions) is determined. Then, some of the glassy samples obtained undergo a structural study, analogously to the glasses of the binary system. The first results about the crystallization tendency of these glasses are obtained.

L’emploi d’adjuvants fluidifiants est courant pour tout béton. Ceci permet d’améliorer les propriétés rhéologiques à l’état frais: la fluidité initiale et son maintien pendant les 2-3 premières heures de la vie d’un béton. La compréhension de ce mécanisme d’action est encore partielle pour les PCP (copolymères greffés). Ici, le but a été de tester l’hypothèse selon laquelle l’évolution de la quantité de PCP adsorbé par unité de surface minérale instantanée explique quantitativement l’évolution temporelle de la fluidité au cours de la période d’ouvrabilité.Sur un système inerte (calcite), nous avons confirmé que la fluidité est bien gouvernée par l’adsorption: à même adsorption surfacique, la fluidité de la pâte est quasiment identique quelle que soit la structure du PCP. Par ailleurs sur un système inerte (calcite ou ettringite), la modification de la fonction ionique du PCP fournit une solution pour améliorer la résistance de l’adsorption à la variation de la concentration en sulfates.Deux techniques ont été utilisées pour mesurer l’aire interfaciale au cours de l’hydratation d’un système réactif modèle (aluminate tricalcique, gypse, hémihydrate et calcite): l’adsorption de N2 et la relaxométrie du proton de l’eau. L’adsorption du PCP par unité de surface réelle a été calculée et corrélée à la fluidité de la pâte. La relation simple fluidité/adsorption n’est plus vérifiée ici. La présence de PCP a un impact sur l’hydratation du système et l’augmentation de l’étendue de la surface minérale associée. Les PCP vont augmenter la surface spécifique de l’ettringite qui précipite en modifiant sa morphologie. Cet effet est plus marqué quand la densité de greffage du PCP diminue. / Nowadays the use of superplasticizers admixtures becomes unavoidable for concrete. It allows enhancing the rheological properties at the fresh state: the initial flow and slump retention during the 2-3 first hours of the life of a concrete. The understanding of this mechanism is still partly elucidated for PCE (grafted copolymers). The aim of this thesis was to challenge the assumption of the evolution of the adsorbed amount of PCE per instantaneous mineral surface unit as origin of the fluidity temporal evolution during the workability period.On an inert system (calcite), we confirmed that the fluidity is mainly governed by the adsorption level. Thus for a same surface adsorption density, the fluidity of the paste is roughly similar whatever the structure of the PCE. On an inert system also (calcite or ettringite), the modification of the anionic function provides a technological way to improve the resistance of the adsorption against the variation of the sulfate ions concentration.The surface area of a reactive model system (tricalcium aluminate, gypsum, hemihydrate and calcite) has been measured by two techniques during the workability period: the N2 adsorption (BET) and the water proton relaxometry (RMN). The PCE adsorption per surface unit has been calculated and analysed in link with the fluidity of the paste. In that case, the simple relation, shown on the inert system, is not verified because the presence of PCE has also an impact on the hydration and on the extent of the surface area. Especially PCE lead to increase the surface by changing the morphology of ettringite. The specific surface area of ettringite increases when the grafting density of PCE decreases.

Du fait de leur ferromagnétisme, les nanoparticules de Cobalt se prêtent à la réalisation d’expérience de Résonance Nucléaire Magnétique en Champ Interne du 59Co (RMN-CI). Dans ce manuscrit, nous présentons tout d’abord une description générale de la RMN-CI dans le cadre du modèle de Bloch. Concernant plus précisément le Co(0), passant en revue la littérature, nous insistons sur les aspects controversés et les progrès récents en la matière. Une attention particulière est portée à la caractérisation du Co dans les catalyseurs Fischer-Tropsch (FT) qui représente aujourd’hui un champ majeur d’application de la technique ; l’histoire de la catalyse FT et une brève revue de la synthèse et de la structure de ces catalyseurs sont donc présentées. Concernant le travail expérimental, celui-ci est structuré de la façon suivante. Tout d’abord, des échantillons modèles sont étudiés afin de mettre en place un modèle interprétatif basé sur les contributions structurales (fcc, hcp, sfs) et magnétiques (domaines, parois de domaines, mono-domaines) à la résonance. Nous passons ensuite à l’étude in situ par RMN-CI de la stabilité thermique de nanoparticules supportées sur du β-SiC. La transition hcp/fcc est observée dans la gamme de température 600-650 K. Ceci étant posé, des structures plus complexes ont été étudiées. Nous avons révélé la structure de la partie métallique de céramiques modifiées Co-Al-O. Finalement, la structure et la stabilité de particules de Cobalt métallique déposées sur et dans des nanotubes de carbone ont été étudiées. Ces structures hybrides originales ont été examinées par RMN-CI, microscopie électronique en transmission et DRX synchrotron in situ. / This manuscript is devoted to the study of different catalysis-related materials by Internal Field 59Co Nuclear Magnetic Resonance (IF-NMR). The principles of IF-NMR are stated, based on the Bloch model, which gives a good insight into the internal field NMR mechanism. Further, a short description of the possible range of materials than can be studied by IF-NMR is provided with a particular emphasis on Co Fischer-Tropsch synthesis catalysts. The study of a model sample used to assess our understanding of IF-NMR spectra is included. This model is based on separating the structural (fcc, hcp, and sfs) and magnetic (domains, domain walls, and single-domain particles) contributions. Our experimental work uncovers the thermal stability of small Co nanoparticles probed in situ by IF-NMR. Co(0) supported on β-SiC is studied within the 300-850 K temperature range. The line position and width are mainly determined by magnetic properties, whereas the absolute and relative NMR intensities give crucial information regarding the Co particle stability. A study of Fischer-Tropsch catalysts synthesized by non-conventional co-precipitation routes on different modified aluminum oxides is presented. The IF-NMR application to Co-Al-O ceramic materials provided unique information on the metallic cermet part of the sample. The structure and stabilization of different size Co(0) nanoparticles on multi-walled carbon nanotubes have been studied. These hybrid structures were examined by IF-NMR, HRTEM, and in situ synchrotron XRD, which provide crucial information on Co particles reduction, stability and structures.

Face à la pénurie de granulats alluvionnaires, l’utilisation de granulats issus de roches massives est devenue systématique pour la formulation de mortiers ou de bétons. Ainsi, la part des granulats concassés de roche massive a fortement augmenté lors de la dernière décennie alors que, pour des raisons normatives dans le domaine du recyclage, la part des granulats recyclés est amenée à le faire lors de la prochaine. La relation de ces granulats avec l’eau et, plus particulièrement, de leur fraction fine est beaucoup plus complexe que celle de leurs prédécesseurs, les granulats naturels alluvionnaires. Ces particules plus poreuses sont à même d’absorber des quantités d’eau plus importantes mais elles le font, par ailleurs, avec des cinétiques peu comparables. Pour contrôler l’absorption d’eau des granulats poreux, il est d’usage de compenser l’absorption des granulats au moment de la formulation après avoir caractériser les granulats. Cependant, l’angularité et la rugosité de surface des granulats recyclés imposent d’adapter les normes actuelles utilisées pour la caractérisation de granulats alluvionnaires. Dans ce travail de thèse, nous proposons de mettre en place différentes méthodes pour caractériser les granulats concassés et recyclés. Dans un premier temps, nous étudions la méthode consistant à déterminer l’absorption d’eau par séchage de granulats saturés et nous montrons que cette méthode est plus particulièrement adaptée dans le cas de granulats de morphologie anguleuse. En effet, nous montrons que la baisse du taux de séchage est bien associée au passage de l’évaporation inter-grains à l’évaporation de l’eau intra-grains et que cette méthode permet une bonne estimation de l’absorption de granulats fins poreux. Dans un second temps, nous montrons que l’étude de la perte de rhéologie d’un mortier, à travers des mesures d’étalement, permet de déterminer l’absorption d’eau de granulats poreux. Nous étendons, dans une deuxième partie, notre étude aux conséquences inhérentes à l’utilisation de ces granulats dans un nouveau matériau cimentaire. Nous observons, à l’aide de la spectrométrie RMN, les transferts d’eau de la pâte de ciment fraîche vers les granulats poreux. Nous observons que l’absorption d’eau de granulats recyclés peut être réduite dans une pâte de ciment fraîche par rapport à l’absorption dans l’eau pure. Nous montrons que le prétraitement thermique généralement imposé en laboratoire aux granulats recyclés impacte la microstructure par la déshydratation d’hydrates tels que les aluminates et les silicates de calcium. En présence de la solution interstitielle de la pâte de ciment, la réhydratation des anhydres peut amener à une précipitation de calcium dans la porosité qui limite l’absorption par colmatage des pores / The environmental threat on non-renewable resources such as rounded natural aggregates strongly affects the materials available for the production of mortar or concrete. This leads to an increase in the relative contribution of alternative resources such as recycled or crushed aggregates. The interaction of water with these inclusions, especially the finest sand particles, is far more complex than in the case of the standard rounded natural aggregates. These alternative particles are indeed able to absorb far more water with very different kinetics than their previous counterparts. In order to take into account aggregates water content and correct the resulting water absorption with the aim of always producing the same material with the same properties, it is usual to correct the amount of mixing water added in the mix-design. However, the traditional standard used to measure rounded aggregates water absorption is not suitable for crushed aggregates. We propose, as a first step, to develop tests allowing for the assessment of water absorption and its kinetics in the case of crushed and recycled sands. To achieve this, we measure rheology losses of mortars by slump flow test and drying kinetics of saturated porous aggregates. We show that these methods are suitable to determine water absorption of crushed or recycled aggregates. In the second phase, we study the consequences of the use of porous aggregates in a new cementitious material. We observe water transfers between aggregates and fresh cement paste using nuclear magnetic resonance. We measure a lower final water absorption in the fresh cement paste than in pure water. We show that oven-drying of recycled aggregates in laboratory can impact cement paste microstructure by hydrates dehydration like calcium silicates or calcium aluminates. The rehydration of anhydrous by interstitial solution of fresh cement paste involves calcium precipitation in the pores and this precipitation can reduce water absorption by clogging aggregates porosity