Résumé : L’auto-cicatrisation des fissures des matériaux cimentaires présente un intérêt important pour améliorer leur durabilité (propriétés de transfert par exemple). L’impact du laitier de haut-fourneau sur ce phénomène a été peu étudié bien qu’il ait été observé sur des ouvrages du Génie Civil. Dans cette étude, la cinétique et l’amplitude de l’auto-cicatrisation ont été suivies par des essais non destructifs : la tomographie aux rayons X et la perméabilité à l’air, pour une fissuration créée à 7 jours et à 28 jours. Les résultats montrent que le laitier de haut-fourneau possède un potentiel d’auto-cicatrisation intéressant pouvant dépasser les résultats obtenus pour les formulations de référence sans laitier. Ce bon potentiel dépend des caractéristiques physico-chimiques des matériaux brutes et du potentiel d’hydratation de la formulation au cours du temps. De plus pour suivre l’auto-cicatrisation, un nouvel essai a été mis en place afin de fissurer les éprouvettes de mortier par retrait gêné et d’étudier l’auto-cicatrisation d’une fissure naturelle. Cet essai s’est avéré efficace sur la formulation de référence. Une caractérisation des produits de cicatrisation par MEB-EDS témoigne de la formation de nouveaux produits dans les fissures et de l’impact important des conditions de stockage sur le type de produits formés: des C-S-H pour un stockage sous eau et des carbonates de calcium pour un stockage en chambre humide (CO2 + eau). Les résultats de migration aux chlorures de nano-indentation montrent que ces produits de cicatrisation possèdent de bonnes propriétés de durabilité et des propriétés mécaniques à l’échelle microscopique intéressantes (pour le carbonate de calcium). Enfin, une modélisation du phénomène d’auto-cicatrisation est proposée au moyen du code de calcul de géochimie PHREEQC. L’étude a révélé le potentiel intéressant de PHREEQC pour modéliser l’auto-cicatrisation et en faire un outil de prédiction du phénomène. / Abstract : Self-healing of cementitious materials presents great interest to improve the durability of concrete structure (transfer properties for example). The impact of blast-furnace slag on this phenomenon is not yet clear even if the self-healing of concrete with blast-furnace slag was observed in building sites. To understand the blast-furnace slag influence, non-destructive methods were used to follow self-healing: X-ray tomography and gas permeability test. All specimens were cracked at 7 days and 28 days. The results show that the blast furnace slag has an interesting self-healing potential that can exceed the reference formulation results. This good potential depends on the physico-chemical characteristics of the raw materials and the hydration potential of the formulation over time. In addition to follow the self-healing, a new trial was set up to crack mortar specimens by restrained shrinkage and study the self-healing of a natural crack. In addition to follow the self-healing, a new trial was set up to crack mortar specimens by restrained shrinkage and study the self-healing of a natural crack. This test has proven effective over the reference formulation.The SEM with EDS analysis showed the formation of new products in the crack and the impact of storage conditions on these products : C-S-H for specimens stored in water and calcium carbonate for specimens stored in a damp chamber (CO2 + water). Migration chlorures and nano-indentation tests results showed that self-healing products had interesting durability properties and micro-mechanical properties (for calcium carbonate). Finally, self-healing modelling is proposed by means of geochemistry PHREEQC calculation code. The study revealed interesting potential PHREEQC to model self- healing phenomenon and make it a of predictive tool.

It is perhaps paradoxical that many material properties arise from the absence of material rather than the presence of it. For example, the strength, stiffness, and toughness of a concrete are related to its pore structure. Furthermore, the volume, size distribution, and interconnectivity of porosity is important for understanding permeability, diffusivity, and capillary action occurring in concrete, which are necessary for predicting service lives in aggressive environments. This research advances the state-of-the-art of multiscale characterization of cement-based materials, and uses this characterization information to model the material behavior under competing durability concerns. In the first part of this research, a novel method is proposed to characterize the entrained air void system. In the second and third parts of this research, microstructural characterization is used in tandem with mechanical models to investigate the behavior of cementitious materials when exposed to rapid rates of loading and to cyclic freezing and thawing. First, a novel analytical technique is presented which reconstructs the 3D entrained air void distribution in hardened concrete using 2D image analysis. This method proposes a new spacing factor, which is believed to be more sensitive to microstructural changes than the current spacing factor commonly utilized in practiced, and specified in ASTM C457, as a measure of concrete's ability to resist to damage under cyclic freeze/thaw loading. This has the potential to improve economy by improving the quality of petrographic assessment and reducing the need for more expensive and time-consuming freeze/thaw tests, while also promoting the durability of concrete. Second, quantitative measurements of the sizes, shapes, and spatial arrangements of flaws which are through to drive failure at strain rates above 100/s were obtained in order to model mortar subjected to high strain-rate loading (i.e., extremes in load rate). A micromechanics model was used to study the ways in which flaw geometry and flaw interaction govern damage. A key finding suggests that dynamic strength may be multimodal, with larger flaws shifting the dynamic strength upwards into the highest strength failure mode. Third, a robust theoretical approach, based upon poroelasticity, is presented to further validate the utility of the novel spacing factor proposed this research. The model is truly multiscale, using in its formulation pore size data ranging from the nanoscale to the micro-scale, entrained air data from the micro-scale to the millimeter scale, and infers a representative volume element on the centimeter scale. The results provide an underlying physical basis for the performance of the novel spacing factor. Furthermore, the framework could be used as a forensic tool, or as a tool to optimize the entrained air void system against freeze/thaw damage.

This work examined the effects of thermal and chemical treatments on zeolite reactivity and determined the zeolite properties governing the development of compressive strengths and pozzolanic reactivity. Zeolites are naturally occurring aluminosilicate minerals found abundantly around the world. Incorporation of zeolites in cement mixtures has been shown by past research to increase concrete’s compressive strength and durability. In addition, use of zeolites as SCMs can decrease the environmental impact and energy demands associated with cement production for reinforced concrete structures. Further, in contrast to man-made SCMs such as fly ash, zeolite minerals provide a reliable and readily available SCM source, not affected by the production limits and regulations of unrelated industries such as the coal power industry. In this work, six sources of naturally occurring clinoptilolite zeolite were examined. The zeolites were first characterized using x-ray fluorescence, quantitative xray diffraction, thermal analysis, particle size analysis, pore size distribution and surface area analysis, and scanning electron microscopy. Cation exchange capacity was also tested for one of the zeolites. Following comprehensive material characterization, the six pozzolanic reactivity of the natural zeolites was determined by measuring the quantity of calcium hydroxide in paste after 28 or 90 days, by measuring calcium hydroxide consumption of the zeolite in solution and by tracking the development of strengths of zeolite-cement mortars. Pretreatments that attempted to increase the reactivity of the zeolites, including calcination, acid treatment, milling and cation exchange, were then tested and evaluated using the same methods of material characterization and testing mentioned previously. Last, the results of the reactivity testing were reanalyzed to determine which properties of natural zeolites, including particle size, nitrogen-available surface area, and composition, govern the development of compressive strengths, pozzolanic reactivity and improved cement hydration parameters of pastes and mortars using natural zeolites as SCMs. Pretreatment testing showed that milling and acid treatment successfully increased the reactivity of zeolites used as SCMs. Additionally, particle size was shown to be the dominant property in determining the development of compressive strengths while particle size and surface area of the zeolites contributed to zeolite pozzolanic reactivity. / text

Doctor of Philosophy / Department of Civil Engineering / Kyle A. Riding / Finely ground glass has the potential for pozzolanic reactivity and can serve as a supplementary cementitious material (SCM). Glass reaction kinetics depends on both temperature and glass composition. Uniform composition, amorphous nature, and high silica content of glass make ground glass an ideal material for studying the effects of glass type and particle size on reactivity at different temperature. This study focuses on how three narrow size ranges of clear and green glass cullet, 63–75 [mu]m, 25–38 [mu]m, and smaller than 25 [mu]m, as well as combination of glass types and particle sizes affects the microstructure and performance properties of cementitious systems containing glass cullet as a SCM. Isothermal calorimetry, chemical shrinkage, thermogravimetric analysis (TGA), quantitative analysis of X-ray diffraction (XRD), and analysis of scanning electron microscope (SEM) images in backscattered (BS) mode were used to quantify the cement reaction kinetics and microstructure. Additionally, compressive strength and water sorptivity experiments were performed on mortar samples to correlate reactivity of cementitious materials containing glass to the performance of cementitious mixtures. A recently-developed modeling platform called “[mu]ic the model” was used to simulated pozzolanic reactivity of single type and fraction size and combined types and particle sizes of finely ground glass. Results showed that ground glass exhibits pozzolanic properties, especially when particles of clear and green glass below 25 [mu]m and their combination were used at elevated temperatures, reflecting that glass cullet is a temperature-sensitive SCM. Moreover, glass composition was seen to have a large impact on reactivity. In this study, green glass showed higher reactivity than clear glass. Results also revealed that the simultaneous effect of sizes and types of glass cullet (surface area) on the degree of hydration of glass particles can be accounted for through a linear addition, reflecting that the surface area would significantly affect glass cullet reactivity and that the effects of SCM material interaction on reaction kinetics were minimal. However, mechanical properties of cementitious systems containing combined glass types and sizes behaved differently, as they followed the weaker portion of the two particles. This behavior was attributed to the pores sizes, distruibution, and connectiity. Simulations of combined glass types and sizes showed that more work on microstructural models is needed to properly model the reactivity of mixed glass particle systems.

As argamassas de revestimento são amplamente utilizadas na construção civil e, suas propriedades no estado endurecido são fortemente influenciadas pelas propriedades no estado fresco, as quais dependem de fatores como: materiais empregados; forma de aplicação; e interação entre substrato e argamassa. Os ensaios utilizados para caracterização reológica das argamassas não contemplam as alterações que ocorrem devido o contato com o substrato, gerando discordâncias nas teorias sobre os fenômenos pelo qual ocorre a resistência de aderência. Sendo assim, o presente trabalho visa identificar as alterações do comportamento reológico de suspensões cimentícias aplicadas em substratos porosos por meio do ajuste do método do squeeze-flow. Para tanto, foram utilizadas duas configurações do squeeze-flow, com e sem confinamento do fluxo radial; três tipos de base, sendo uma metálica e duas porosas; e, pastas com diferentes materiais, a saber: cimento; cal e filler calcário. A escolha da pasta ao invés da argamassa foi basicamente por duas razões: primeiro, porque a pasta é a parcela da argamassa mais suscetível aos efeitos de sucção capilar do substrato; e segundo, para simplificar o cenário de análise, eliminando a variável areia. Ambas as configurações apresentaram-se viáveis na identificação da alteração do comportamento reológico da pasta, devido aos fatores como: tipo de substrato; o tempo de contato entre pasta e substrato; perda de água da pasta; e energia de mistura. Além disso, observou-se que os procedimentos adotados, assim como o auxílio de outros ensaios, podem colaborar em estudos da influência de fatores como: temperatura; rugosidade; ângulo de contato; distribuição granulométrica de pastas e argamassas; e, principalmente, compreender os fenômenos que ocorre no período denominado como tempo de puxamento, ao passo que este influencia diretamente na resistência de aderência. / Mortar renderings are used in most of the constructions and their properties in the hardened state are strongly influenced by the properties in the fresh state, which depend on factors such as materials used; application form; and interaction between substrate and mortar. The determination of rheological parameters of fresh mortars doesn\'t include the changes that occur due to contact with the substrate. It generates disagreements in the theories about the phenomena of formation of the bond strength. Therefore, this study aims to identify changes in the rheological behavior of cementitious paste applied to porous substrates by adjusting the squeeze flow method. For this, two configurations of squeeze flow were used, with and without confinement of the radial flow; three substrate types; and pastes with different materials, namely cement, lime and sand. The choice of paste instead of mortar was basically for two reasons: first, because the paste is the portion of mortar more susceptible to the effects of capillary suction of substrate; and second, to simplify scenario analysis, eliminating the variable sand. Both configurations were viable in the identification of the alteration of rheological behavior of paste, due to factors such as substrate type; the contact time between paste and substrate; loss of water from paste; and mixing energy. In addition, it was observed that the procedures adopted as well as the aid of the other tests can collaborate on studies of the influence of factors such as temperature, roughness, contact angle, particle size distribution of pastes and mortars; and above all to understand the phenomena that occurs in the initial periods of contact paste/substrate and consequently in the bond strength.

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.

A utilização de fibras vegetais como reforço de matrizes frágeis de cimento é justificada pelo baixo custo, alta disponibilidade, principalmente em países como o Brasil, que possui agricultura desenvolvida, boas condições edafo-climáticas e grandes áreas para cultivo. No entanto, em razão da alta alcalinidade do cimento a matriz reforçada tem a durabilidade comprometida pela degradação das fibras. Uma medida para minimizar esse ataque alcalino é a dissolução da lignina e da hemicelulose das fibras, menos resistentes em condições de pH elevado, através da polpação química, processo que individualiza as fibras celulósicas, que podem ser utilizadas como reforço de compósitos cimentícios em substituição parcial às fibras sintéticas. As polpas aplicadas para este fim são comumente produzidas pelo processo Kraft. Uma alternativa mais limpa a este processo é a polpação organossolve que usa reagentes orgânicos durante o cozimento e proporciona facilidade para recuperação do solvente no final do processo. O bambu possui fibras de elevada resistência mecânica, portanto sua utilização como matéria-prima para produção de polpas celulósicas é justificada por ser um material viável, de fácil aplicação, rápido crescimento e pronta disponibilidade. A proposta deste trabalho foi a produção de polpa de bambu pelo processo organossolve utilizando as variáveis tempo x temperatura com a finalidade de encontrar a condição ótima para o processo, de forma que houvesse melhor rendimento e que as características químicas, físicas e morfológicas da polpa fossem compatíveis às exigidas para utilização como reforço de matrizes cimentícias. A melhor condição foi o cozimento a temperatura de 190ºC durante 2 h. O tempo de 1 h de cozimento foi insuficiente para a solubilização da lignina e o período de 3 h é inviável devido a degradação da cadeia de celulose. Foram produzidos pelo método de sucção a pressão negativa, compósitos com matriz de cimento com substituição parcial de metacaulim e testados os teores de 6, 8, 10 e 12% de polpa de bambu como reforço. O teor de polpa definido como ideal foi 8%, o mesmo encontrado na literatura para polpa Kraft de bambu. Produziram-se placas com duas composições. Uma com substituição parcial de 25% do cimento por metacaulim e a segunda com substituição de 25% do cimento por calcário moído. Os compósitos contendo metacaulim foram submetidos a envelhecimento acelerado por meio de 50, 100 e 200 ciclos de imersão e secagem para avaliação da durabilidade. As propriedades físicas foram melhoradas com os ciclos de envelhecimento, ocasionando diminuição na porosidade aparente pela migração dos produtos da hidratação do cimento para a zona em torno das fibras, e, em consequência, melhorias nas propriedades mecânicas de módulo de ruptura (MOR), limite de proporcionalidade (LOP) e módulo de elasticidade (MOE), tanto para a substituição parcial do cimento por metacaulim como para calcário. Houve diminuição na energia específica (EE) com os ciclos de imersão e secagem, justificada pela maior aderência entre fibra-matriz. Observados os parâmetros de polpação organossolve adotados para o bambu, essa polpa apresenta-se viável para reforço de matrizes inorgânicas a base de cimento Portland. / The use of natural fibers as reinforcement for brittle cement matrices is justified by the its low cost, high availability, especially in countries like Brazil, which has developed agriculture, good soil and climatic conditions and large areas for cultivation. However, due to the high alkalinity of cement the reinforced matrix has it durability compromised by the fiber degradation. One measure to minimize this alkaline attack is the dissolution of lignin and hemicellulose fibers, that are less resistant under conditions of high pH, by chemical pulping, that is a process that individualizes the cellulosic fibers, which can be used as reinforcement of cementitious composites in partial replacement synthetic fibers. The pulps applied for this purpose are commonly produced by the kraft pulping process. A cleaner alternative to this process is the organosolv pulping that use organic reagents during cooking and provides facility for solvent recovery at the end of the process.The bamboo fibers have high mechanical strength, therefore their use as raw materials for production of cellulose pulps is justified because it is a viable material, easily applied, rapid growth and ready availability. The purpose of this study was the production of bamboo pulp by the organosolv process using the variables time vs temperature in order to find the optimum condition for the process, so that there was a better yield and that the chemical, physical and morphological characteristics of the pulp were compatible to those required for use as reinforcement in cementitious matrices. The best condition was the cooking temperature of 190ºC for 2 h. The time of 1 h of cooking was insufficient to solubilize the lignin and the time of 3 h is infeasible due to degradation of the cellulose chain. The composites with matrix of cement and with partial replacement of metakaolin were produced by the method of negative pressure suction and tested the levels of 6, 8, 10 and 12% bamboo pulp as reinforcement. The pulp content was defined as an ideal 8%, as found in the literature for bamboo Kraft pulp. The plates were produced with two compositions. One with partial substitution of cement by 25% of metakaolin and the second with 25% replacement of cement by limestone. The composites containing metakaolin were subjected to accelerated ageing through 50, 100 and 200 wet and dry cycles for durability evaluation. The physical properties were improved with the ageing cycles, decreasing the porosity by migration of the cement hydration products to the zone around the fibers and, consequently, improvements in mechanical properties of modulus of rupture (MOR), limit proportionality (LOP) and modulus of elasticity (MOE) for both the partial replacement of cement by metakaolin as for limestone. The decreased of the specific energy (EE) with the wet and dry cycles was due to the higher adhesion between fiber-matrix. With the observation of the parameters adopted for bamboo organosolv pulping, this pulp has to be feasible for reinforcement of inorganic matrices based in Portland cement.

Une solution pour réduire l’impact environnemental du béton est de substituer une partie du ciment par des additions minérales, comme le laitier de hauts fourneaux. Néanmoins, cette substitution ne doit pas réduire les performances du matériau vis-à-vis de la carbonatation, l’un des principaux phénomènes de vieillissement des structures en béton armé. La carbonatation est une réaction chimique entre la matrice cimentaire et le dioxyde de carbone présent dans l’air. Cette réaction, en plus de former du carbonate de calcium, diminue le pH de la solution interstitielle rendant ainsi les armatures vulnérables à la corrosion. Les essais accélérés de carbonatation montrent, en laboratoire, une grande disparité de comportements entre matériaux cimentaires très faiblement poreux à hautes performances mécaniques et matériaux plus poreux en usage dans les ouvrages courants. L’objectif de cette thèse est de mieux comprendre le phénomène de carbonatation des matériaux cimentaires, notamment ceux contenant du laitier de hauts-fourneaux. Nous avons procédé en découplant les phénomènes impliqués dans la carbonatation que sont la diffusion gazeuse, les réactions chimiques et les transferts hydriques (séchage). La première partie de ces travaux de thèse a nécessité le développement et la validation d’un dispositif de mesure expérimental du coefficient de diffusion du CO2. Ce dernier a permis une étude paramétrique sur pâtes mettant en évidence l’influence de la composition et de la carbonatation sur la diffusion. La seconde partie a porté sur l’étude des cinétiques de carbonatation de pâtes en fonction du degré de saturation, après une mise à l’équilibre hydrique sur une longue période. Ces cinétiques ont été étudiées, sur échantillons de faibles dimensions, au moyen d’un suivi des évolutions pondérales et d’analyses thermogravimétriques, pour l’identification des hydrates résiduels et des carbonates formés. Nous avons ainsi mis en évidence des différences de comportement des hydrates et des liants vis-à-vis de la carbonatation impliquant la microstructure du matériau. / One solution for reducing the environmental impact of concrete is to substitute a part of cement by mineral additions, such as granulated blast furnace slag. However, this substitution should not reduce the performances of concrete with respect to carbonation, one of the main ageing phenomena of reinforced concrete structures. Carbonation is a chemical reaction between the cement matrix and the carbon dioxide from the atmosphere. In addition to the formation of calcium carbonate, this reaction results in a pH reduction of the pore solution and a risk of corrosion. Laboratory accelerated tests show a wide disparity between the carbonation resistance of high mechanical performances concretes with low porosity and the resistance of more porous and more usual ones. The objective of this thesis is to better understand the phenomenon of carbonation of cementitious materials, including those containing blast furnace slags. This work was carried out by decoupling the phenomena involved in carbonation that are gaseous diffusion, chemical reactions and water transfers. First, an experimental device for measuring the CO2 diffusion coefficient was developed. After validation, the latter was used in a parametric study carried out on cement pastes showing the influence of composition and carbonation on the diffusion coefficient. The second part of the thesis work focused on studying the kinetics of carbonation of pastes with respect to the degree of water saturation. Prior to carbonation, the studied pastes were conserved during a long period at various RH to achieve hydric equilibrium. The carbonation kinetics of small size samples of pastes was studied by means of monitoring of weight changes and thermogravimetric analyzes for identification of residual hydrates and formed carbonates. We have thus shown differences in behavior of hydrates and binders during carbonation involving the material microstructure.

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.