Ce travail expérimental a porté sur la dégradation de deux matériaux cimentaires, un mortier (pour la grande majorité des essais) et un béton, suite à un chauffage intense jusqu’à 600°C et parfois 700°C. L’idée qui a sous tendu cette étude était de « mesurer » cette dégradation via les propriétés de transport : la perméabilité au gaz et la porosité au gaz sous contrainte de confinement et certaines propriétés poro-mécaniques. Pour mener à bien ce travail, plusieurs techniques expérimentales ont été développées ou améliorées. Il s’agit en particulier de la mesure de porosité au gaz sous contrainte de confinement. L’emploi d’un gaz neutre permet de remplir les vides connectés dans le matériau et de calculer sa porosité. La réhydratation avec de l’eau déminéralisée a un effet considérable sur les matériaux fortement chauffés car elle restaure une grande partie de la porosité qui retrouve son niveau initial voire parfois une valeur inférieure à celui-ci. Très logiquement le « self-healing » permet aussi de restaurer une large part de la perméabilité qui ne retrouve cependant pas son niveau initial. / This experimental work focused on the degradation of two cementitious materials, mortar (for most tests) and a concrete following an intense heating to 600 ° C and 700 ° C sometimes. The idea that underpinned the study was to "measure" this degradation via the transport properties : gas permeability and porosity to gas under confining stress and some poro-mechanical properties. To carry out this work, several experimental techniques have been developed or improved. This is particularly the porosity measurement gas under a confining stress. The use of a neutral gas is used to fill the voids in the material and connected to calculate its porosity. Rehydration with demineralized water has a considerable effect on the highly heated material because it restores much of the porosity which regains its initial level or sometimes a value less than one. Logically the "self-healing" also restores much of the permeability which does not recover its original level

Submitted by JOSIANE SANTOS DE OLIVEIRA (josianeso) on 2018-08-08T16:43:38Z No. of bitstreams: 1 Ana Júlia Maciel Marinho Fernandes_.pdf: 24903248 bytes, checksum: e58f36fcc0799fa5830bd2beede0f0ac (MD5) / Made available in DSpace on 2018-08-08T16:43:38Z (GMT). No. of bitstreams: 1 Ana Júlia Maciel Marinho Fernandes_.pdf: 24903248 bytes, checksum: e58f36fcc0799fa5830bd2beede0f0ac (MD5) Previous issue date: 2018-05-28 / Nenhuma / A utilização de materiais cimentícios suplementares (MCS) na produção de cimento é uma estratégia bastante difundida para diminuição de custos de produção, e pode contribuir para a minimização da emissão de CO2. Estes materiais, ao reagirem com o hidróxido de cálcio (CH), gerado na hidratação do cimento, formam silicatos de cálcio e aluminatos de cálcio hidratados adicionais, contribuindo para o ganho de resistência. Segundo a normativa brasileira, para ser considerado um material pozolânico, o somatório de óxidos de Si, Al e Fe deve ser maior do que 70%. No entanto este requisito deve ser tomado com restrições, pois evidências indicam que somente a fração amorfa dos óxidos pozolânicos é que consomem CH. Diante disto, este trabalho teve por objetivo geral avaliar de forma comparativa a influência da composição química e da fração amorfa dos óxidos pozolânicos na reatividade de materiais cimentícios suplementares. Foram estudados uma cinza volante da combustão do carvão (CV); de um resíduo de cerâmica vermelha (RCV); e de um metacaulim (MK). Os materiais tiveram a granulometria ajustada a fim de se obter um D50 de 4 ± 2 µm, buscando uma menor diferença entre a distribuição granulométrica dos MCS e o pó de quartzo (PQ), empregado para compor um padrão secundário de referência, o que permite isolar o fator consumo de cimento nas análises. Os MCS foram caracterizados por FRX, por granulometria à laser, por adsorção de nitrogênio, por picnometria de gás hélio, e microscopia eletrônica de varredura. Empregou-se também DRX em conjunto com o refinamento de Rietveld, utilizando-se o método do padrão interno para a quantificação de fases. A reatividade dos MCS foi medida pelo método de Fratini, por TG/DTG e por resistência à compressão, em pastas e argamassas. Constatou-se que todos os MCS são reativos. O teor de amorfos totais em geral não explica o consumo de CaO, nem as resistências de argamassas. O teor de alumina amorfa apresenta considerável influência sobre consumo de CH, medido em análise térmica, em relação à pasta com PQ. O emprego de pastas para ensaios de resistência, e o padrão com PQ, permitiu avaliar a contribuição da reação dos MCS para as resistências, e, neste caso o teor de amorfos totais e de Al2O3 amorfa apresentam a mesma tendência de comportamento, quanto maior o teor, maior a resistência. No entanto, esta tendência não foi observada quando o teor de SiO2 é isolado, pois o RCV não segue o mesmo comportamento. Foi observado também que o teor elevado de Fe2O3 do RCV pode ser o responsável pela baixa redução de CaO observada no ensaio de Fratini deste MCS. / The use of supplementary cementitious materials (SCM) in the cement production is an usually strategy to reduce costs, and it can promote the reduce of the CO2 emissions. These materials react with the calcium hydroxide (CH), generated in the cement hydration, forming hydrated calcium silicates and aluminates, contributing for the compressive strength. A pozzolanic material has to have, according the Brazilian Standards, a sum of Si, Al and Fe oxides above 70%. However, this requirement have to be taken in account with caution, as evidences indicate that only the amorphous fraction of the pozzolanic oxides consume CH. The aim of this work is to evaluate in a comparative way the influence of the chemical composition and of the amorphous fase of pozzolanic oxides in the reactivity of supplementary cementitious materials. It was studied a fly ash from coal burning (FA), a fired-clay brick powder (FCP) and a comercial metacaulim (MK). The size distribution of the material was adjusted in order to obtain a D50 of 4 ± 2 µm, in order to adjust the granulometry of the materials with the quartz powder (QP), that was employed in a secondary reference composition. The use of this secondary reference allows to compare the pozzolanic materials mixtures with a reference with the same cement consumption. The SCM were characterized by XRF, by laser granulometry, by nitrogen adsorption method, helium gas pycnometry, and by scanning electronic microscopy. It was also employed XRD associated with Rietveld refinement, using the internal pattern method for phase quantifying. The SCM reactivity was measured by Fratini Method, by TG/DTG and by compressive strength, in cement pastes and mortars. It was found that all SCM are reactions. The total amorphous content in general does not explain the CaO consumption, neither the mortars strength. The amorphous alumina content shows a considerable influence on the CH consume measured by TG, taking as reference the pastes with QP. The use of cement paste for compressive strength tests, as well the reference with QP, allowed to evaluate the contribution of the reactivity of SCM for the strength, and, in this case, the total amorphous content and the amorphous Al2O3 content presented the same tendency of behaviour: as big is the content, as big is the strength. However, this tendency it was not observed when the amorphous SiO2 is isolated, because the FCP does not have the same behaviour. It also was observed that the high content of Fe2O3 in the FCP can be responsable for the low tax of CaO consumption observed in the Fratini method of this SCM.

Today, with increasing global awareness and regulation of air pollution, interest in the smog-abating property of photocatalytic materials is increasing. Titanium dioxide (TiO2) is the most well known photocatalytic semiconductor and is often considered as one way of solving pollution by a passive but an effective way, particularly to reduce atmospheric nitrogen oxides (NOx=NO+NO2). This relatively new technology is already being used in some of the countries as a construction material, commercially sold as photocatalytic cement, photocatalytic pavement, self-cleaning tiles, and self-cleaning glass. Prior research has examined the photocatalytic properties of TiO2 itself, as well as TiO2-containing cement-based materials. The majority of this effort has been on characterizing and enhancing the photocatalytic efficiency. However, relatively little research was performed to assess the potential impact of the photocatalytic reaction on the "parent" or "host" material. In this research, the focus is on the effect of photocatalysis on the composition, structure, and properties of cementitious materials, which contain titania nanoparticles at early and late ages. Fundamental examinations on the addition of these chemically non-reactive nanoparticles to cement-based materials are performed. The high surface area of nanoparticles could alter early age properties of cementitious materials, such as setting time, dimensional stability, and hydration rate. Various experimental techniques as well as mathematical modeling were used to examine and explain the early age hydration of cementitious materials when TiO2 nanoparticles are present. Further, the effects of the TiO2 on the long term durability of cement-based materials are investigated to demonstrate their suitability for long-term use in the field. The photocatalytic NOx oxidation efficiency and NOx binding capability of TiO2 containing cementitious materials are experimentally investigated. The durability of TiO2-cement is examined by various techniques on samples that went through extensive photocatalysis and environmental exposures. These investigations have led to tentative conclusions on the use of TiO2 nanoparticles in cementitious materials, and suggest avenues for future study.

Most concrete produced today utilizes pozzolans or supplementary cementitious materials (SCMs) to promote better long term durability and resistance to deleterious chemical reactions. While other pozzolans and SCMs are available and provide many of the same benefits, Class F fly ash has become the industry standard for producing quality, durable concrete because of its low cost and wide-spread availability. With impending environmental and safety regulations threatening the availability and quality of Class F fly ash, it is becoming increasing important to find viable alternatives. This research aims to find natural, lightly processed, alternatives to fly ash that perform similarly to Class F fly ash with regards to pozzolanic reactivity and provide comparable compressive strength, workability, drying shrinkage, thermal expansion properties and resistance to alkali-silica reaction, sulfate attack, and chloride ion penetration. Eight fly ash alternatives from the US were tested for compatibility with the governing standard for pozzolans used in portland cement concrete and various fresh and hardened mortar and concrete properties. The results of this research indicate that six materials meet the requirements for natural pozzolans set by the American Society for Testing and Materials and many are comparable to Class F fly ash in durability tests. The primary concern when using these materials in concrete is the increase in water demand. The spherical particle shape of fly ash provides improved workability even at relatively low water-to-cement ratios; however, all of the materials tested for this research required grinding to achieve the appropriate particle size, resulting in an angular and rough surface area that requires more lubrication to achieve a workable consistency. So long as an appropriate water reducing admixture is used, six of the eight materials tested in this study are appropriate and beneficial for use in portland cement concrete. / text

The primary aim of this research was to investigate the fundamental acoustic properties of several cementitious materials, the influence of mix design parameters/constituents, and finally the effect of the physical and mechanical properties of cementitious material concrete/mortar on the acoustic properties of the material. The main objectives were: To understand the mechanism of sound production in musical instruments and the effects of the material(s) employed on the sound generated; To build upon previous research regarding selection of the tested physical/mechanical properties and acoustic properties of cementitious materials; To draw conclusions regarding the effect of different constituents, mix designs and material properties upon the acoustic properties of the material; To build a model of the relationship between the acoustic properties of a cementitious material and its mix design via its physical/mechanical properties. In order to meet the aim, this research was conducted by employing the semi-experimental (half analytical) method: two experimental programmes were performed (I and II); a mathematical optimization technique (least square method) was then implemented in order to construct an optimized mathematical model to match with the experimental data. In Experimental Programme I, six constituents/factors were investigated regarding the effect on the physical/mechanical and acoustic properties: cementitious material additives (fly ash, silica fume, and GGBS), superplasticizer, and basic mix design parameters (w/c ratio, and sand grading). 11 properties (eight physical/mechanical properties: compressive strength, density, hardness, flexural strength, flexural modulus, elastic modulus, dynamic modulus and slump test; and three acoustic properties: resonant frequency, speed of sound and quality factor (internal damping)) were tested for each constituents/factors related mortar type. For each type of mortar, there were three cubes, three prisms and three cylinders produced. In Experimental Programme I, 20 mix designs were investigated, 180 specimens produced, and 660 test results recorded. After analysing the results of Experimental Programme I, fly ash (FA), w/b ratio and b/s ratio were selected as the cementitious material/factors which had the greatest influence on the acoustic properties of the material; these were subsequently investigated in detail in Experimental Programme II. In Experimental Programme II, various combinations of FA replacement level, w/b ratios and b/s ratios (three factors) resulted in 1122 test results. The relationship between these three factors on the selected 11 properties was then determined. Through using regression analysis and optimization technique (least square method), the relationship between the physical/mechanical properties and acoustic properties was then determined. Through both experimental programmes, 54 mix designs were investigated in total, with 486 specimens produced and tested, and 1782 test results recorded. Finally, based upon well-known existing relationships (including, model of compressive strength and elastic modulus, and the model of elastic modulus and dynamic modulus), and new regressioned models of FA-mortar (the relationship of compressive strength and constituents, which is unique for different mixes), the optimized object function of acoustic properties (speed of sound and damping ratio) and mix design (proportions of constituents) were constructed via the physical/mechanical properties.

La digestion anaérobie est une succession d’étapes de dégradation de la matière organique, par l’intermédiaire de microorganismes, opérée industriellement dans des digesteurs en béton. Des métabolites microbiens (acides gras volatils (AGV), NH4+, CO2) produits au cours du processus de digestion attaquent la matrice cimentaire du béton. Afin d’assurer un développement pérenne de la filière de méthanisation, il est donc nécessaire de comprendre d’abord tous ces phénomènes d’altération pour ensuite proposer des solutions durables pour les matériaux de construction des digesteurs. Les objectifs de la thèse visaient à identifier et quantifier les agents agressifs pour le béton présents dans les milieux de la méthanisation, puis à comprendre leurs rôles dans les mécanismes d’altération des matrices cimentaires. Enfin, l’action de ces milieux a pu être comparée sur un panel de matériaux cimentaires réalisées à partir de différents liants : ciment Portland ordinaire, ciment de haut-fourneau, ciment d’aluminate de calcium et liant alcali activé. Dans des digesteurs de laboratoire, les concentrations maximales des agents chimiques agressifs mesurées pendant la digestion anaérobie d’un biodéchet modèle étaient de 3000 mg.L-1 d’AGV, de 800 mg.L-1 de NH4+, et de 140 mg.L-1 de CO2 dissous. La prolifération de microorganismes capables de métaboliser ces composés chimiques agressifs a été observée à la surface des matériaux cimentaires exposés dans le biodéchet au cours de sa digestion. La zone dégradée des matériaux cimentaires exposés est partiellement décalcifiée, vraisemblablement du fait de l’action des AGV et de l’ammonium NH4+, et carbonatée en raison de la présence de CO2 dissous. Des essais in situ, c’est à dire en conditions réelles, réalisées sur une plateforme expérimentale de méthanisation, ont permis de confirmer les phénomènes d’altération observés en laboratoire. En termes de durabilité, le ciment alumineux présente la meilleure résistance face aux attaques biochimiques lorsqu’on le compare au ciment ordinaire ou aux ciments composés de laitier de haut-fourneau au sein de systèmes de méthanisation en laboratoire ou in situ. / Anaerobic digestion consists in the degradation of organic matter by the successive actions of microorganisms, industrially operated in digesters made of concrete. Microbial metabolites (volatile fatty acids (VFA), NH4+, CO2) produced during this process attack the cementitious matrix of the concrete. To ensure the development of this new industrial field, it appears essential to understand first the alteration phenomena, then to propose durable solutions for digesters’ construction materials. The thesis’ objectives were first to identify and to quantify the aggressive agents for concrete in anaerobic digestion media, then to understand their impacts on the cementitious materials’ alteration mechanisms. Finally, the impacts of those media were compared on different cement pastes made of : ordinary Portland cement, blast furnace slag cement, calcium aluminate cement or alkali activated materials. During laboratory tests, the maximal concentration in aggressive agents measured during the digestion of a synthetic biowaste were 3 000 mg.L-1 of VFA, 800 mg.L-1 of NH4+, and 140 mg.L-1 of dissolved CO2. The colonization of the microorganisms able to produce the aggressive agents has been observed on the cementitious materials’ surfaces exposed to the biowaste during digestion. The external degraded layers of the exposed cementitious materials are partially decalcified, most likely regarding to the action of the VFA and the NH4+. Carbonation has also been detected caused by the dissolved CO2. In situ experiments, in real conditions, achieved in an experimental anaerobic digestion platform, confirmed the alteration phenomena distinguished in the laboratory tests. In terms of durability, calcium aluminate cement present the best performances against the biochemical attacks compared to ordinary cement or blast furnace slag cement in laboratory or in situ anaerobic digestion systems.

A engenharia de materiais proporcionou os avanços mais notórios sobre o desempenho mecânico dos materiais cimentícios nas últimas décadas, ora por meio das técnicas de conformação, ora pelo projeto da microestrutura. Com isso, demonstrou-se ser falsa a idéia de que baixas resistências mecânicas seriam inerentes aos materiais cimentícios, mas, ao mesmo tempo, o restrito advento desses novos materiais aos setores de maior demanda os relegou à condição de alternativos apenas. O fato de cada tonelada de cimento Portland gerar outra tonelada de gases do efeito estufa indica que o quadro anterior precisa ser revisto. É por isso que uma das principais contribuições desse trabalho foi desenvolver a conformação por técnicas altamente produtivas e capazes de propiciar excelente desempenho mecânico, além da durabilidade, aos materiais cimentícios. A concepção e a construção de uma linha de prensagem por rolos foi o primeiro passo para que as placas cimentícias com resistência à compressão superior à 200MPa e reprodutibilidade compatível à das cerâmicas técnicas fossem obtidas de modo eficaz. Por sua vez, a extrusão, uma técnica capaz de produzir perfis com geometrias complexas e em grande quantidade, também foi bem adaptada aos materiais cimentícios, com excelente reprodutibilidade e resistência à flexão superior à 20MPa. Em ambas, prensagem e extrusão, o domínio da técnica nos permitiu obter componentes cimentícios cujas resistências mecânicas não sofrem influências de quaisquer que sejam os ambientes ao quais são expostos. A isso atribuímos o mais amplo conceito de durabilidade para um material cuja utilização depende da resistência mecânica ao longo de sua vida útil. Ainda, um método inovador para a durabilidade desses materiais foi desenvolvido neste trabalho: trata-se de sua impregnação por TEOS, um precursor de sílica molecular que reage com o hidróxido de cálcio para selar os poros pelos quais penetrou. Em números, significa a possibilidade de reduzir a porosidade dos corpos à base de cimento Portland para valores inferiores a 1% em volume, ao que se associa à concomitante redução de uma ordem de grandeza no coeficiente de difusão do íon cloro. Em resumo, os resultados que serão apresentados estão em ressonância com os mais rigorosos critérios de sustentabilidade num setor que urge por melhores perspectivas para o definitivo ingresso na era da industrialização: a construção civil. Porém, a maior virtude deste trabalho é não apenas aprimorar as etapas da engenharia dos materiais cimentícios, mas também aplicar a ciência para o entendimento da origem de sua resistência mecânica. De acordo com nossas comprovações experimentais, a resistência mecânica desses materiais é governada pelas moléculas de água confinadas em películas nanométricas entre as fases que se hidratam do cimento Portland. Essas moléculas de água se comportam como uma fase vítrea e, por sua vez, promovem adesão às superfícies que a confinam. Essa é também uma contribuição deste trabalho para tornar viável a nanotecnologia desses materiais por intermédio de um tema até então inexplorado: a adesão por água confinada. Acreditamos também que o grau de inovação sobre esse tema poderá extrapolar o material em si, visto que a vida como conhecemos é uma conseqüência direta das intrigantes propriedades da água e suas ligações hidrogênio. / The materials engineering afforded the most paramount known advances on the mechanical performance of cementitious materials in the last decades, through either casting techniques or microstructure design. Therewith, it was demonstrated to be false the idea that low mechanical strengths should be inherent to cement-based materials, but, at the same time, the limited ingress of these new materials to fields of great demands relegated them to the condition of merely alternative. The fact that each ton of Portland cement does create another ton of gases related to global warming indicates that the former situation needs to be reviewed. That is why one of the main contributions of this work was to improve casting techniques to render massive production and excellent mechanical performance, in addition to durability, for the cementitious materials. The concept and the construction of a roll compaction equipment were the first step to the cost-effective production of cementitious plates with compressive strength in excess of 200MPa, in addition to a reproducibility inasmuch as that of a technical ceramic. In the same way, the extrusion, a technique able to largely produce components of complex geometries, was also well adapted to cement-based materials which, again, showed excellent reproducibility and bending strength of more than 20MPa. In both, pressing and extrusion techniques, the control of processing steps was enough to get cement-based products whose mechanical strength barely changes, even after exposure to deleterious environments. Hereby, we attribute the widest concept of durability to a material which depends on the mechanical strength throughout its service life. Anyway, we also developed an innovative method to improve the durability of these materials along this work: TEOS impregnation. TEOS is a molecular precursor of silica which reacts with calcium hydroxide to seal the cementitious pores wherefrom it penetrated. Quantitatively, the porosity of Portland cement-based products dropped down to values around 1% in volume, what is related to concomitant reduction of chlorine ion diffusion coefficient of an order of magnitude. In summary, the results that will be demonstrated in the following chapters are in resonance with the most rigorous rules for sustainability, precisely in a field where such an initiative is welcome to help encouraging its industrialization: the building construction. However, it seems that the biggest virtue of this work is not only the improvements for cementitious materials engineering, but also to apply the science for the understanding of the origin of their mechanical strength. According to our experimental evidences, the mechanical strength of these materials is ruled by water molecules which are confined in nanometric layers between the hydrating phases of Portland cement. These water nanolayers behave themselves as glassy phase and, in their turn, promote adhesion to the surfaces which confine them. To the best of our knowledge, this work is one of the most promising contributions to become possible the nanotechnology of these materials, through a subject up to that time unexplored: the adhesion by confined water. Hence, it is likely that the innovation about this subject could exceed the material itself, once life as we know owes its peculiarities to the intrigant properties of water and to their hydrogen bonding.

Pour ajuster la rhéologie des matériaux cimentaires et modifier leurs principales propriétés d'écoulement, l'utilisation des polymères organiques est nécessaire. L'objectif de cette thèse est de définir un cadre général physique permettant de caractériser qualitativement les conséquences de l'introduction d'un ou plusieurs polymères dans une pâte de ciment. De façon à s'affranchir des spécificités chimiques de chaque molécule, nous prenons le parti d'adopter une approche physique générale dans laquelle un polymère est défini par sa localisation (en solution ou à la surface d'un grain) et par sa taille caractéristique (en solution ou à la surface d'un grain). Nous sélectionnons des polymères couvrant la gamme de molécules disponibles lors de la formulation d'un matériau cimentaire : super-plastifiants, agents de viscosité, retardateurs de prise, floculants. Dans un premier temps, nous étudions le comportement des polymères dans le fluide interstitiel d'une pâte de ciment. Nous mesurons leurs rayons hydrodynamiques en solution et leur influence sur la viscosité du fluide interstitiel d'une pâte de ciment. Nous montrons qu'au premier ordre, la conformation, en régime dilué, de la majorité des polymères étudiés ici et tirés de la littérature, peut être décrite par la même courbe maitresse en fonction de la masse molaire. Nous identifions la fraction volumique des polymères en solution comme le paramètre principal qui est à même de capturer la physique dominante et commune à la majorité des polymères étudiés ici et régissant leur comportement macroscopique en solution. Nous étudions ensuite le comportement des polymères dans une pâte de ciment. Nous mesurons leur adsorption à la surface des particules de ciment et nous analysons les résultats obtenus dans deux régimes asymptotiques de la littérature: le régime d'adsorption à faible taux de couverture de surface et le régime d'adsorption à la saturation qui nous donnent respectivement des informations sur l'affinité intrinsèque du trio polymère/surface/solvant et sur la conformation des polymères adsorbés à la saturation. Nous discutons alors les valeurs d'affinité et d'adsorption à la saturation mesurées à la lueur des paramètres et des structures moléculaires de nos polymères. Dans une troisième partie, nous rappelons les origines physiques microscopiques du comportement rhéologique d'une pâte de ciment. Nous identifions, dans le cas où les polymères n'introduisent pas de nouvelles forces dans le système deux paramètres principaux, la distance inter-particulaire et la viscosité du fluide interstitiel, qui peuvent être ajustés par l'ajout de polymères et entrainer des changements majeurs dans la rhéologie d'une pâte de ciment standard. Dans une dernière partie, nous étudions la compétition d'adsorption entre polymères à la surface des particules de ciment. Nous proposons tout d'abord un protocole expérimental basé sur des mesures de diffraction dynamique de la lumière nous permettant de distinguer les adsorptions respectives de deux polymères sur une même surface. Nous illustrons ensuite la compétition d'adsorption et l'utilisation potentielle qui peut être faite de cette technique en étudiant successivement les compétitions d'adsorption entre un super-plastifiant et trois autres espèces adsorbantes : des ions sulfates, un retardateur de prise et un agent de viscosité. Nous montrons que, selon le taux de couverture de surface, cette compétition peut être plus au moins marquée et ses conséquences rhéologiques plus au moins drastiques. L'approche physique proposée ici consistant à ignorer autant que possible les spécificités chimiques des macromolécules étudiées atteint, à plusieurs occasions, ses limites. Lorsque c'est le cas, nous regroupons à la fin des parties concernées les discussions et analyses des situations où l'introduction d'un polymère dévie de la réponse générique au premier ordre obtenue pour l‘ensemble des autres macromolécules étudiées / To fulfil the rheological requirements of cementitious materials, mix designer engineers use various polymers. Theses admixtures either stay in the suspending fluid modifying its viscosity or adsorb at the surface of cement particles modifying their surface properties and their interactions. In this work, we propose a general physical frame allowing for the description of the consequences of the addition of one or various polymers on the rheology of cement paste. We identify two main parameters affecting the rheology of cement paste, which can be modified by chemical admixtures. These parameters are the inter-particle distance and the viscosity of the suspending fluid. Our solution viscosity and hydrodynamic radii measurements in synthetic cement pore solution suggest that the volume fraction of polymers is the main parameter enhancing the viscosity of the suspending fluid. By means of rheological and adsorption measurements, we study the effects of polymers on the inter-particle distance and the rheological behavior of the suspension. Finally, we study the competitive adsorption between polymers at the surface of cement particles. We propose a technique based on dynamic light scattering measurements allowing for the measurement of the respective adsorption of two polymers at the surface of cement particles. We then study the competitive adsorption between a super-plasticizer and sulfate ions, retarder or viscosity enhancing admixtures

Dès les premières utilisations des matériaux cimentaires, l'ajout de fibres a permis de renforcer ces matrices fragiles. Ces fibres, comme pour tout autre type d'inclusions, modifient les propriétés rhéologiques du matériau à l'état frais. Dans un premier temps, nous étudions spécifiquement l'influence de l'ajout des fibres sur le seuil d'écoulement de matériaux cimentaires. Nous considérons des écoulements suffisamment brefs pour que l'orientation des fibres soit négligeable. Nous montrons que, comme dans le cas d'inclusions sphériques, il existe une fraction volumique critique de fibres pour laquelle un réseau percolé de contacts directs entre inclusions se forme. Nous déduisons de ce constat une méthode permettant de prédire la quantité de fibres pour laquelle une augmentation de plusieurs ordres de grandeurs du seuil du matériau a lieu. Nous dérivons de cette étude des critères de formulation utilisables dans la pratique industrielle. Nous étendons dans un deuxième temps notre étude aux systèmes anisotropes de façon à prédire l'évolution de l'orientation des fibres lors de coulages industriels standards. Pour cela nous construisons et comparons des outils expérimentaux, analytiques ou numériques permettant respectivement de mesurer et de prédire l'orientation des fibres en fonction des caractéristiques des fibres, du comportement rhéologique du mélange et du procédé de mise en œuvre. Nous montrons que la majorité des écoulements industriels peut se réduire à des écoulements simples pour lesquels le processus d'orientation est décrit en première approximation par les travaux de Jeffery. Des zones mortes dans lesquelles la contrainte est inférieure au seuil du matériau conservent leur isotropie initiale. Nous montrons qu'à l'échelle d'un coulage industriel, l'orientation des fibres peut être considérée comme instantanée. Les méthodes étudiées s'avèrent capables de prédire l'orientation induite par les écoule ments expérimentaux / Fibers have always been added to cementitious materials in order to reinforce the brittle nature of the matrix. As for any other type of inclusions, fiber addition modifies the rheological behavior of the material in the fresh state. In a first part, we focus on the influence of fiber addition on the yield stress of cementitious materials. We only consider flows which are too short or with no steady streamlines for orientation to affect the behavior of the material. We show that, as for spherical inclusions, a critical fiber volume fraction leads to the formation of a percolation network between all the inclusions. Predictions of this critical volume fraction can be derived from experimental measurements, leading to a sudden increase of several orders of magnitude in yield stress. Industrial mix design criteria are finally proposed. This work is extended in a second part to anisotropic systems. We then focus on the prediction of fiber orientation during standard industrial castings. Tools are built and compared from experimental, analytical and numerical approaches in order to measure and predict fiber orientation as a function of fiber characteristics, suspension rheological behavior and casting process. It is shown that most industrial flows can be considered as simple flows during which fiber orientation process is, as a first approximation, described by the Jeffery theory. In plug flow zones, where stress is lower than the material yield stress, the initial isotropy is conserved. We show that, at the time scale of the casting process, fiber orientation can be considered as instantaneous. It is finally concluded that analytical and numerical methods used in this work enable to predict orientation induced by the flows experimentally validated

Ce travail s'inscrit dans le contexte des recherches menées pour la modélisation des composites aléatoires, permettant de déterminer leurs propriétés mécaniques effectives (élasticité et résistance). Parmi les modèles micromécaniques, numériques ou analytiques, développés dans ce but, on retrouve certains qui prennent en compte les effets d'interfaces se produisant aux frontières des inclusions des composites. Ces interfaces ont, selon plusieurs auteurs, une grande influence sur les propriétés élastiques et de rupture. Les modèles les considérant à ce jour sont néanmoins limités aux cas d'inclusions sphériques ou cylindriques. Dans cette thèse, nous proposons plusieurs approches et modèles micromécaniques (ou multi-échelles) qui permettent de déterminer les propriétés élastiques et poroélastiques ainsi que les modes de ruptures de matériaux composites granulaires présentant divers effets d'interfaces. Les morphologies inclusionnaires étudiées ne se limitent pas à la forme sphérique mais s'étendent également aux inclusions ellipsoïdales ce qui nous a amené à examiner une rupture inter-granulaire anisotrope. Les modèles de rupture développés dans ce travail ont été appliqués aux gels de C-S-H (hydrates de la pâte de ciment) ce qui a permis d'améliorer les modèles de rupture consacrés aux pâtes durcies. Les prédictions de ces modèles ont pu être confrontées à des données expérimentales de résistance à la compression simple des pâtes / Modelling composite media in view of determining its effective mechanical behaviour has been the topic of a large number of research papers. Some analytical and numerical models that can be found in the scientific literature on this topic take into account the interface effects that can arise at inclusions' boundaries. These interfaces have a major influence on the mechanical properties of composites according to some researchers. However, the models considering them are limited to spherical and cylindrical inclusions. In this work, several multi-scale approaches and models are developed to consider interface effects in the determination of the effective elastic and poroelastic properties and the failure mechanisms of granular composites. These models are performed on both spherical and ellipsoidal shapes of inclusions. The latter has led us to investigate an anisotropic inter-granular failure in granular media. The failure models developed in this work are applied to the microstructure of C-S-H gels (a cement paste hydrate) in order to improve the existing models on cement paste failure. The predictions of these improved models are compared to experimental data on the compressive strength of cement pastes