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An Energy Based Nanomechanical Properties Evaluation Method for Cementitious MaterialsJha, Kaushal K 31 May 2012 (has links)
Advances in multiscale material modeling of structural concrete have created an upsurge of interest in the accurate evaluation of mechanical properties and volume fractions of its nano constituents. The task is accomplished by analyzing the response of a material to indentation, obtained as an outcome of a nanoindentation experiment, using a procedure called the Oliver and Pharr (OP) method. Despite its widespread use, the accuracy of this method is often questioned when it is applied to the data from heterogeneous materials or from the materials that show pile-up and sink-in during indentation, which necessitates the development of an alternative method.
In this study, a model is developed within the framework defined by contact mechanics to compute the nanomechanical properties of a material from its indentation response. Unlike the OP method, indentation energies are employed in the form of dimensionless constants to evaluate model parameters. Analysis of the load-displacement data pertaining to a wide range of materials revealed that the energy constants may be used to determine the indenter tip bluntness, hardness and initial unloading stiffness of the material. The proposed model has two main advantages: (1) it does not require the computation of the contact area, a source of error in the existing method; and (2) it incorporates the effect of peak indentation load, dwelling period and indenter tip bluntness on the measured mechanical properties explicitly.
Indentation tests are also carried out on samples from cement paste to validate the energy based model developed herein by determining the elastic modulus and hardness of different phases of the paste. As a consequence, it has been found that the model computes the mechanical properties in close agreement with that obtained by the OP method; a discrepancy, though insignificant, is observed more in the case of C-S-H than in the anhydrous phase. Nevertheless, the proposed method is computationally efficient, and thus it is highly suitable when the grid indentation technique is required to be performed. In addition, several empirical relations are developed that are found to be crucial in understanding the nanomechanical behavior of cementitious materials.
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Étude expérimentale et modélisation de l'auto-cicatrisation des matériaux cimentaires avec additions minérales / Experimental study and modelisation of self-healing cementitious materials with mineral additionsOlivier, Kelly 14 January 2016 (has links)
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 physicochimiques 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. / 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.
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Etudes expérimentales et numériques des matériaux cimentaires sous sollicitations hydro-mécaniques / Experimental and numerical investigations of cementitious materials under hydro-mechanical loadingsSoleilhet, François 13 March 2018 (has links)
Les matériaux cimentaires sont les plus utilisés dans les ouvrages du génie civil. Que ce soit dans les domaines de l'habitation, des transports ou bien encore de l'énergie, ils sont utilisés massivement et doivent faire face à un environnement varié et parfois agressif. Le béton, particulièrement lorsqu'il est armé, est un matériau qui de part son fonctionnement est amené à fissurer. Outre l'aspect visuel qui peut attirer l'attention des utilisateurs, la fissuration impacte, en premier lieu la résistance mécanique mais aussi la durabilité de l'ouvrage. Une meilleure caractérisation de cette fissuration (quantité, trajet, tortuosité) est donc un enjeu majeur. Pour répondre à cette problématique, il est nécessaire de prédire le comportement à long terme des ouvrages. Néanmoins, cette tâche reste ardue. La grande hétérogénéité du matériau combinée aux sollicitations multiples (thermique, chimique, hydrique, mécanique) rend l'œuvre complexe. Si on s'intéresse plus spécifiquement aux sollicitations hydriques, on constate que toute structure tend à s'équilibrer avec son milieu ambiant entraînant un phénomène de dessiccation. L'objectif de ce travail de thèse est de prendre en compte les effets de cette dessiccation dans la détermination des propriétés mécaniques et du comportement macroscopique des ouvrages en béton (à l'échelle de l'échantillon de laboratoire) afin de mettre en place un cadre de modélisation éléments finis prédictif prenant en compte la dessiccation et les phénomènes associés. Conventionnellement, lorsque les propriétés mécaniques du béton sont caractérisées, les contraintes internes ne sont pas considérées et les phénomènes de dessiccation ne sont pas pris en compte. Néanmoins, le gradient hydrique entre la surface et le cœur d'une structure en béton peut mener à un état de contrainte hétérogène et engendrer une micro-fissuration conséquente. Dans certains cas (durabilité, étanchéité), ce phénomène peut-être d'une importance majeure. Bien qu'il semble remarquable, l'impact du séchage et de la micro-fissuration sur les propriétés mécaniques n'est que peu étudié. De plus, les résultats obtenus sont parfois contradictoires ce qui ne permet pas de dégager de consensus. Il est notable que dans la description du phénomène, trois facteurs prépondérants peuvent être dégagés. L'un d'eux, la pression capillaire, améliore la résistance du matériau et les deux autres, le gradient hydrique ainsi que l'incompatibilité de déformation entre la pâte et les granulats, vont diminuer les caractéristiques mécaniques à long terme. Peu d'études comparent l'influence de la dessiccation sur les propriétés mécaniques en mettant en regard les résultats obtenus suivant les différentes méthodes de caractérisations standards. Ce travail de thèse développe, des campagnes expérimentales investiguant les effets de la dessiccation sous humidité relative, température et temps de dessiccation variés. Il se poursuit par la mise en place du cadre de simulation numérique s'appuyant sur les expériences réalisées. Ces dernières sont modélisées mécaniquement en tenant compte du processus de dessiccation. La prise en compte du retrait de dessiccation, du développement du fluage propre et de dessiccation ainsi que l'apport de la pression capillaire permet de retrouver les résultats expérimentaux mécaniques. De ces simulations mécaniques, des faciès et des ouvertures de fissure sont extraits du modèle continu en se basant sur la théorie de la bande de fissuration. Enfin, des outils d'identification sont développés dans ce cadre afin de déterminer les propriétés des différents modèles numériques. / Cementitious materials are the most used material in civil engineering fields. Whether in the areas of housing, transport or energy, they are used heavily and have to face a varied and sometimes aggressive environment. Concrete, especially when it is reinforced, is a material which by its operation is caused to crack. In addition to the visual aspect that can attract the attention of users, cracking impacts, primarily the mechanical strength but also the durability of the structure. A better characterization of this cracking (quantity, path, tortuosity) is therefore a major issue.To answer this problem, it is necessary to predict the long-term behavior of structures. Nevertheless, this task remains arduous. The great heterogeneity of the material combined with multiple stresses (thermal, chemical, hydric, mechanical) makes the work complex. If one is interested more specifically in the hydric solicitations, one finds that any structure tends to equilibrate with its environment causing a phenomenon of drying.The aim of this thesis is to take into account the effects of drying on the mechanical properties and the macroscopic behavior of concrete structures (at the laboratory sample scale) in order to set up a predictive finite element modelling framework taking into account drying and associated phenomena. Conventionally, when the mechanical properties of concrete are characterized, internal stresses are not considered and drying phenomena are not taken into account. Nevertheless, the hydric gradient between the surface and the core of a concrete structure can lead to a state of heterogeneous stress and generate a consequent micro-cracking. In some cases (durability, tightness), this phenomenon may be of major importance.Although it seems remarkable, the impact of drying and micro-cracking on mechanical properties is poorly studied. In addition, the results obtained are sometimes contradictory which does not allow to reach consensus. It is notable that in the description of the phenomenon, three overriding factors can be identified. One of them, the capillary pressure, improves the resistance of the material and the two others, the water gradient as well as the incompatibility of deformation between the paste and the aggregates, will decrease the mechanical characteristics in the long term.Few studies compare the influence of desiccation on mechanical properties by comparing the results obtained using different standard characterization methods. This thesis work develops experimental campaigns investigating the effects of drying under relative humidity, temperature and drying time varied. It continues with the implementation of the numerical simulation framework based on the experiments carried out.These are modelled mechanically taking into account the drying process. Taking into account the withdrawal of desiccation, the development of clean creep and desiccation as well as the contribution of the capillary pressure makes it possible to recover the experimental mechanical results. These mechanical simulations, facies and crack openings are extracted from the continuous model based on the crack band theory. Finally, identification tools are developed in this context to determine the properties of different numerical models.
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Poromechanical behavior of cement-based materials subjected to freeze-thaw actions with salts : modeling and experiments / Comportement poromécanique des matériaux cimentaires soumis au gel-dégel en présence de sels : modélisation et expérimentationZeng, Qiang 30 November 2011 (has links)
Les matériaux cimentaires peuvent se détériorer grandement lorsqu'ils sont soumis à des cycles de gel/dégel avec ou sans sels de déverglaçage. Ceci peut porter atteinte à la durabilité à long terme des bétons/mortiers dans les régions aux hivers froids. Laissant de côté les processus d'endommagement et de rupture mécanique à l'oeuvre dans de tels problèmes, ce mémoire de thèse est consacré aux phénomènes physiques et thermo-mécaniques accompagnant la solidification de l'eau dans des solides poreux cohésifs, avec une attention particulière aux «propriétés matériau» issues de l'hydratation du ciment et de l'évolution de la microstructure. Ce travail reprend la poromécanique des milieux poreux partiellement gelés telle que développée par Olivier Coussy, tout en lui adjoignant une analyse de l'effet de la fin de la surfusion (en volume, hors contribution capillaire) et de la présence de sels dans le liquide saturant l'espace poreux. Nous avons mesuré la température de fin de surfusion en fonction de la concentration en sel. Ceci nous permet ensuite de calculer l'angle de contact entre la glace et les parois des pores dans le cadre classique de la nucléation hétérogène : on trouve que cet angle diminue avec la concentration en sel. Nous montrons que la dilatation instantanée consécutive à la fin de la surfusion dépend de la structure poreuse puisque cette dernière détermine la teneur en glace dans l'espace poreux. À l'aide de la distribution de tailles de pores estimée par porosimétrie par intrusion de mercure, nous estimons le degré de saturation en glace en fonction de la température et de la concentration initiale en sel via la relation de Gibbs-Thomson. Nous avons mesuré la déformation d'échantilllons de pâte de ciment saturées. L'analyse poromécanique montre que la déformation dépend de la concentration initiale en sel et de la structure poreuse des pâtes de ciment. En utilisant la même approche expérimentale sur des pâtes de ciment sèches, nous trouvons que la porosité (avec ou sans vide d'air entraîné) influence significativement le coefficient d'expansion thermique du matériau. En ce qui concerne les pâtes de ciment saturées, les mesures expérimentales et l'approche poromécanique en condition drainée ou non-drainée montrent que le degré de saturation initiale en liquide des vides d'air entraîné a un impact important sur la déformation de l'échantillon avec la température / When subject to freezing/thawing cycles with or without deicing salt, cement-based materials can suffer severe damage, which raises the long term sustainability problem of concrete/mortar in cold regions. Leaving aside the precise fracture mechanics and damage processes in this kind of problem, this PhD deals with the physical and thermomechanical phenomena undergone by cohesive porous solids under freezing, with particular attention to the material properties arising from cement hydration and microstructure development. The present work revisits the poromechanics of freezing porous materials developed by Olivier Coussy. This gives the opportunity to add the effect of the bulk supercooling and of salt in the liquid saturating the porous space.We measured the relation between depressed temperature at the end of bulk supercooling and salt concentration. We then obtained that the contact angle between ice and pore wall by heterogeneous nucleation decreases as salt concentration increases. We showed that the instantaneous dilation at the end of bulk supercooling is related to the pore structure because the latter determines the in-pore ice content. Using the pore size distribution measured by mercury intrusion porosimetry, we estimated the ice saturation degree with temperature and NaCl solution at different concentration through the Gibbs-Thomson equation. We measured the deformation of saturated cement pastes. The poromechanical analyses show that the strains depend on the initial salt concentration and pore structure of our cement pastes. By the same experimental approach on dried cement pastes, we concluded that the porosity (with or without air voids) has significant influence on the thermal expansion coefficient of our cement pastes. We also performed measurements on the deformation of saturated air entrained cement pastes. The results obtained by both experiments and poromechanical analyses under drained and undrained conditions showed that the initial saturation degree in air-voids has significant influence on the deformation curves with temperature
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Estudo de propriedades de pastas e argamassas cimentícias compostas com vermiculita brasileira (in natura e calcinada). / Study of properties of cementitious pastes and mortars made with Brazilian vermiculite (in natura and calcined).Rojas-Ramírez, Roberto Antonio 13 November 2018 (has links)
No processo de beneficiamento da vermiculita é gerado um resíduo fino para o qual atualmente ainda não foi desenvolvida uma aplicação que possibilite a utilização em larga escala. Uma alternativa que vem sendo estudada é a associação com cimento Portland em composições de argamassas e concretos, em função da composição química do resíduo: elevada quantidade de alumínio, silício e magnésio, que podem apresentar interações com o ligante. No entanto, em função da elevada área superficial específica, em comparação ao cimento, sua utilização nas composições pode afetar a demanda de água de amassamento e limitar a sua aplicação. Para tanto, uma alternativa é a calcinação deste resíduo fino, assim como é realizado para outras argilas (caulim, por exemplo), para que a área superficial específica (ASE) seja menor e eventualmente ative propriedades pozolânicas na respectiva argila. Deste modo, neste trabalho foram avaliadas as diversas características de pastas cimentícias após adição de resíduo fino de vermiculita: reação química, formação dos produtos hidratados, propriedades reológicas, tanto após a mistura como ao longo da hidratação. Foi verificado que de forma geral a reação química não é afetada após a adição de vermiculita, embora a formação de aluminatos seja intensificada na composição com maior quantidade de resíduo in natura. Com relação ao seu comportamento no estado fresco, foi observado que a maior ASE do resíduo impacta fortemente as propriedades reológicas das pastas, embora que com um teor de 5% as mudanças sejam menores. Utilizando-se dessas mesmas composições para a avaliação do desempenho no estado endurecido de argamassas, foi verificado que não há efeito sobre essas propriedades até 5% de substituição, independentemente do tratamento térmico empregado. Assim, considerando aspectos econômicos de transporte assim como os custos decorrentes da calcinação, pode-se recomendar a adição de 5% de vermiculita in natura sem comprometer o desempenho dos produtos, embora não se possa precisar com os dados obtidos a sua durabilidade ao longo do uso. / In the process to obtaining vermiculite a fine residue is generated, which does not yet have a large-scale application. An alternative that has been studied is the association with Portland cement in mortar and concrete formulations, as a function of the chemical composition of the residue: high amount of aluminium, silicon and magnesium which may have interactions with the binder. However, the residue has a high specific surface area, in comparison to cement, a fact that can increase the water-demand to mix and limit its application. For this, an alternative is the calcination of this fine residue, as it is done for other clays (kaolin, for example), so that the specific surface area (SSA) is smaller and eventually activates pozzolanic properties in the respective clay. Thus, in this work the various characteristics of cement pastes after addition of vermiculite fine residue were evaluated: chemical reaction, formation of the hydrated products, rheological properties, both after mixing and along the hydration. It was verified that in general the chemical reaction is not affected after the addition of vermiculite, although the formation of aluminates is intensified in the composition with greater amount of in nature residue. Regarding its behaviour in the fresh state, it was observed that the higher SSA of the residue strongly impacts the rheological properties of the pastes, although with a 5% content the changes are minimal. Using these same compositions to evaluate the performance in the hardened state of mortars, it was verified that there is no effect on these properties up to 5% of substitution, regardless of the thermal treatment used. Thus, considering the economic aspects of transport as well as the costs of calcination, it is possible to recommend the addition of 5% of vermiculite in nature without compromising the performance of the products, although it is not possible to determine the its durability during the use.
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Etude de l’effet de la composition de la solution interstitielle des matériaux cimentaires sur les interactions multi-espèces lors des transferts de chlorures / Study of the effect of pore solutions chemistry of the cementitious materials on the multispecies interactions during chlorides transferCherif, Rachid 16 January 2018 (has links)
La durabilité des ouvrages en béton armé est étroitement liée à la composition des matériaux dont ils sont formés, et plus particulièrement aux propriétés de ces derniers. Cette durabilité est caractérisée par des indicateurs parmi lesquels se trouve le coefficient de diffusion des chlorures. Ceux-ci pénètrent le béton et interagissent avec les ions composant la solution interstitielle (contenue dans les pores) ainsi que les composants de la matrice cimentaire. Il existe peu de travaux dans la littérature qui décrivent toutes ces interactions ioniques de façon simultanée et encore moins leur prise en compte dans l’étude et la modélisation des transferts. Ce travail de thèse présente une étude des interactions multi-espèces se produisant lors du transfert des ions chlorure. Pour ce faire, l’évolution de la composition de la solution interstitielle, de plusieurs pâtes de ciment contenant diverses additions minérales, est étudiée. La solution interstitielle des pâtes de ciment est extraite suite à un essai de migration par pressage et analysée par chromatographie ionique. Par ailleurs, l’évolution de la microstructure de ces matériaux suite au transfert des chlorures est caractérisée par porosimétrie à intrusion de mercure (PIM) et microscopie électronique à balayage (MEB). Ceci a permis de mettre en évidence les modifications provoquées par la diffusion des ions chlorures. Dans un second temps, et afin de simuler le transfert des chlorures dans la matrice cimentaire, un modèle de transfert multi-espèces est développé. Dans ce sens, plusieurs modèles de transfert mono et multi-espèces, sous l’effet d’un champ électrique ou non, en régime stationnaire et transitoire ont été développés auparavant. L’objectif de cette partie numérique est d’étendre ces modèles à la prise en compte de l’ensemble des ions composant la solution interstitielle ainsi que leurs interactions multi-espèces conduisant à la précipitation de composés à base de chlore et à la dissolution des hydrates. La formulation mathématique des phénomènes étudiés est établie à partir de la loi de conservation de masse et les équations de la thermodynamique. Les conditions initiales et aux limites sont adaptées pour tenir compte à la fois de la composition chimique réelle de l’eau de mer et de celle de la solution interstitielle. Les résultats obtenus permettent de mettre en exergue l’effet de ces phénomènes sur la composition chimique de la solution interstitielle ainsi que sur le transfert des chlorures. / The durability of the reinforced concrete structures is closely related to the composition of their materials and, particularly to their properties. This durability is characterized by indicators among which we quote the diffusion coefficient of chlorides. These ionic species penetrate through the concrete and interact with the other species present in the interstitial solution (contained in concrete pores) as well as the cementitious matrix components. In the literature, there is a lake of data describing simultaneously these ionic interactions, especially their consideration in the study or modeling the ionic transport phenomena. This work focuses on the study of multispecies interactions that occur during the chloride transfer. To this purpose, the evolution of pore solutions chemistry of hardened cement pastes manufactured with different mineral additions is investigated. This solution is extracted, before and after migration test, using a specific press and analyzed by ionic chromatography. Furthermore, the microstructure evolution of these cement pastes is characterized by mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). This allows highlighting the modification caused by chloride penetration. Secondly, for the modeling of chloride transport in cement based materials, a multispecies transport model is developed. In this context, several mono and multispecies transport models, under an electrical field or not, in transitory or steady state were developed previously. The aim of this numerical study is to extend these models in order to consider the ions present in the interstitial solution and their multispecies interactions leading to the precipitation of new chloride compound and the dissolution of some hydrates. The mathematical formulation of the phenomena studied was established from the principle of mass conservation and the thermodynamic equations. Initial and boundary conditions were adopted to take into account both the chemical composition of sea water and that of pore solution. Results highlight the effect of these phenomena on the pore solution chemistry and the chloride transport.
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O uso de pozolanas como materiais cimentícios suplementares: disponibilidade, reatividade, demanda de água e indicadores ambientais. / Pozzolan as supplementary cementitious materials: avaiability, reactivity, water demand and environmental indicators.Pedro Cesar Rodrigues Alves Abrão 07 December 2018 (has links)
O cimento está entre os materiais mais utilizados no mundo moderno e sua produção deverá crescer nos próximos 40 anos. Esta crescente produção será responsável pela emissão de um grande volume de CO2 na atmosfera, atualmente a indústria cimenteira é responsável mundialmente por 10% das emissões totais de CO2 e pode chegar a 30% em 2050. Portanto, a academia e a indústria estão desenvolvendo estratégias para reduzir este impacto ambiental, uma dessas estratégias é a substituição do clínquer por materiais cimentícios suplementares (MCSs). Para esta estratégia ser efetiva é necessário que estes materiais possuam: (i) viabilidade econômica; (ii) disponibilidade e; (iii) viabilidade técnica. Hoje os materiais suplementares mais utilizados são a escória de alto forno e a cinza volante, mas o aumento na produção do cimento não foi acompanhado pela oferta destes materiais. Assim, outros materiais suplementares estão sendo utilizados pela indústria, como é o caso das pozolanas naturais e artificiais. Portanto o objetivo deste trabalho é estimar a disponibilidade e distribuição geográfica de alguns materiais cimentícios suplementares no Brasil e avaliar a eficiência de seis cimentos pozolânicos comerciais e compará-los com um cimento com alto teor de clínquer quanto a reatividade, demanda de água e indicadores ambientais. Todos os materiais foram fisicamente e quimicamente caracterizados; pastas e argamassas foram analisadas em termos de reatividade, demanda de água e resistência mecânica; finalmente, foram estimados indicadores ambientais e de eficiência. Para pastas e argamassas sem dispersante o cimento com alto teor de clínquer e aqueles com adição de terra diatomácea demandaram mais água que os demais para um mesmo espalhamento, já com adição de superplastificante o cimento REF foi o que demandou mais água. O cimento com alto teor de clínquer foi o mais reativo em todas as idades e apresentou os melhores resultados do indicador de fração de água combinada e indicador de intensidade de ligante. Já para o indicador intensidade de carbono os melhores resultados foram obtidos para os cimentos com alto teor de substituição. No entanto, o estudo mostra que a redução do teor de clínquer não está diretamente relacionada à redução do impacto ambiental do cimento em seu uso, esta redução de impacto também está associada com a eficiência do ligante quanto a sua reatividade e demanda de água. / The cement is one of the most used materials in the modern world and its production should grow in the next 40 years. This growing production will be responsible for issuing a large volume of CO2 on the atmosphere, nowadays the cement industry is responsible worldwide for 10% of the total emissions of CO2 and it can reach 30% in 2050. Therefore, academia and industry are developing strategies to reduce this environmental impact, one of these strategies is the substitution of clinker by supplementary cementitious materials (SCMs). For this strategy to be effective it is necessary that these materials possess: (i) economic viability; (ii) availability and; (iii) technical feasibility. Today the most used supplementary materials are the blast furnace slag and fly ash, but the increase in the production of cement was not accompanied by the supply of these materials. Therefore, other supplementary materials are being used by the industry, as is the case of natural and artificial pozzolans. So, the aim of this work is to estimate the availability and geographic distribution of some supplementary cementitious materials in Brazil and evaluate the efficiency of six Portland pozzolan blended cements and compare them with a cement with high clinker content as to reactivity, water demand and environmental indicators. All materials were physically and chemically characterized; pastes and mortars were analyzed in terms of reactivity, water demand and mechanical strength; finally, environmental and efficiency indicators were estimated. For pastes and mortars without dispersant the cement with high content of clinker and those with the addition of diatomaceous earth ordered more water than the others to achieve the same spread, already with the addition of superplasticizer the cement REF was the one that ordered more water than the others. The cement with high clinker content was the most reactive in all ages and presented the best results of the binder efficiency indicator and binder intensity indicator. For the carbon intensity indicator, the best results were obtained for cements with high replacement content. However, the study shows that the reduction of the clinker content is not directly related to the reduction of the environmental impact of the cement in its use, this reduction is also associated with the binder efficiency in means of reactivity and water demand.
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Avaliação de parâmetros químicos e mineralógicos de materiais cimentícios suplementares na mitigação da reação álcali agregadoGuillante, Patricia 16 August 2018 (has links)
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Previous issue date: 2018-08-16 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Estruturas de concreto situadas em ambientes úmidos, produzidas com cimentos com elevado teor de álcalis e agregados reativos, estão propensas a desencadear uma reação química conhecida como a Reação Álcali-Agregado (RAA). Na tentativa de minimizar o desencadeamento desta reação, pode-se controlar o teor de álcalis, embora isso não seja garantia da não ocorrência da RAA, utilizar agregados não reativos, ou ainda utilizar adições minerais. O grande benefício das adições minerais, especialmente as pozolanas, na mitigação da RAA, está associado ao fato das mesmas consumirem hidróxido de cálcio para formarem silicato de cálcio hidratado adicional, reduzindo a permeabilidade e a mobilidade de álcalis. No entanto, têm-se visto que os materiais pozolânicos sílicoaluminosos apresentam desempenho superior aos materiais silicosos, na RAA, tendo como consenso o papel protagonista da presença de alumínio. No entanto, o comportamento na mitigação da RAA pode ser distinto, dependendo do tipo de pozolana empregada. Assim, o objetivo geral deste trabalho é avaliar a influência dos parâmetros químicos e mineralógicos de materiais cimentícios suplementares na mitigação da RAA. Empregou-se o método acelerado das barras de argamassa para investigar o comportamento de três MCS ricos em sílica e alumina: a Cinza Volante (CV), o Metacaulim (MK) e o Resíduo de Cerâmica Vermelha (RCV). Foram consideradas duas idades de cura – 48h e 28 dias – e empregou-se ainda, misturas auxiliares com sílica ativa em teor semelhante ao de sílica amorfa presente nos MCS; com pó de quartzo, para compor um padrão secundário de referência, permitindo avaliar o efeito da redução de consumo de cimento; e, para balizar a avaliação do teor de alumina, misturas com hidróxido de alumínio [Al(OH)3]. Os materiais foram caracterizados quanto aos parâmetros físicos, químicos e mineralógicos. Analisou-se ainda, a composição química da solução aquosa dos poros das diferentes misturas e a microestrutura das barras de argamassa de referência após o ensaio acelerado. O agregado foi classificado como uma obsidiana composta basicamente por vidro vulcânico e os resultados do ensaio acelerado indicam que os MCS empregados apresentam potencial mitigador, porém em diferentes níveis. Constatou-se que, embora nas amostras curadas por 28 dias tenha ocorrido ligeiro aumento das expansões, o tempo de cura não exerceu influência significativa nos resultados. Ao incorporar Al(OH)3, observou-se um comportamento linear das expansões, de modo que quanto maior o teor de Al(OH)3 menores são os valores de expansão. Entretanto, este comportamento não foi verificado com os materiais pozolânicos. O teor total de alumina caracterizado para MK, CV e RCV, foi na ordem de 38%, 21% e 17%, respectivamente, retornando expansões aos 28 dias de ensaio de 0,03%, 0,02% e 0,08%. Destaca-se que os menores resultados de expansão foram observados na mistura com CV, que, por sua vez, apresentou concentração de alumínio na solução dos poros próximo à zero. Sabe-se que a alumina atua na inibição da dissolução da sílica reativa, através da sua incorporação na estrutura de sílica, formando uma espécie de zeólita e, assim, a caracterização da solução dos poros da CV pode ser também um indicador da maior efetividade da alumina da CV na mitigação da RAA. Ainda, observou-se, para a mistura com RCV, que o teor de ferro, principalmente o identificado na forma hematita, parece interferir na dissolução da alumina o que pode ter prejudicado o potencial de mitigação da RAA pela alumina neste caso. Além disso, a forma cristalina ou amorfa de como estes elementos estão presentes nos MCS parece influenciar no potencial de mitigação. Assim, acredita-se que não somente o teor de alumina exerça influência na redução das expansões, mas também os minerais e a estrutura cristalina na qual o alumínio se apresenta no material podem ser indicativos da sua incorporação nas partículas de sílica. / Concrete structures produced with cements of high alkali content and reactive aggregates, when located in humid environments are prone to develop a chemical reaction known as the Alkali-Aggregate Reaction (AAR). In order to minimize the development of this reaction, the alkali content can be controlled by the use of non-reactive aggregates, although this does not guarantee the reaction complete mitigation. Another alternative is the use of mineral additions, especially pozzolans, whose benefit is associated with the fact that it consume calcium hydroxide to produce additional hydrated calcium silicate, reducing the permeability and mobility of alkalis inside concrete. Recent researches have shown that aluminosilicate pozzolanic materials present higher performance in AAR mitigation than siliceous materials. It is consensus that aluminum presence have a protagonist role. However, the mitigation behavior of AAR may be different depending on the type of pozzolanic material employed. Thus, the general objective of this work was to evaluate the influence of chemical and mineralogical parameters of aluminosilicate pozzolans in the mitigation of AAR. The accelerated mortar bars method was used to investigate the behavior of three mineral admixtures rich in silica and alumina: Fly Ash (FA), Metakaolin (MK) and Red Ceramic Waste (RCW). Two curing ages were considered - 48h and 28 days - and auxiliary mixtures with silica fume were used, with similar content of amorphous silica; with powder quartz to compose a secondary reference standard, allowing the evaluation of cement consumption reduction effect; and, to mark the evaluation of the aluminum content, mixtures with aluminum hydroxide [Al(OH)3]. The materials were characterized for physical, chemical and mineralogical parameters. The chemical composition of the pores aqueous solution of the mixtures and the microstructure of the reference mortar bars after the accelerated test were also analyzed. The aggregate was classified as an obsidian composed basically of volcanic glass and the results of the accelerated test indicate that the used pozzolans present mitigating potential, but at different levels. It was found that the curing time had no significant influence on the results, despite the slight increase of expansions measured in samples cured for 28 days, before the accelerated test. By incorporating Al(OH)3, a linear behavior of expansions was observed in which as higher the content of Al(OH)3, the lower the expansion values are. However, this behavior was not verified with the pozzolanic materials. The total aluminum content for MK, FA and RCW was 38%, 21% and 17%, respectively, resulting in expansions at the 28 day test of 0.03%, 0.02% and 0.08%. It is noteworthy that the lower expansion results were observed in the mixture with FA, which also presented aluminum concentration in the pore solution close to zero. It is known that alumina acts in the inhibition of the reactive silica dissolution by its incorporation in the silica structure, forming a kind of zeolite and, therefore, the characterization of the solution of the pores of the FA can also be an indicator of the greater effectiveness of the alumina from FA in the mitigation of AAR. In addition, it was observed that the mixture with RCW that the iron content, mainly identified in the hematite form, seems to interfere in the dissolution of the aluminum, which may have hampered the AAR mitigation potential by aluminum in this case. The crystalline or amorphous form of how these elements are present in pozzolans seem to influence the potential for mitigation. Thus, it is believed that not only the alumina content exerts influence on the expansion reduction, but also its mineral and crystalline structure, in which the aluminum present in the material may indicate its incorporation into the silica particles.
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Estudo de propriedades de pastas e argamassas cimentícias compostas com vermiculita brasileira (in natura e calcinada). / Study of properties of cementitious pastes and mortars made with Brazilian vermiculite (in natura and calcined).Roberto Antonio Rojas-Ramírez 13 November 2018 (has links)
No processo de beneficiamento da vermiculita é gerado um resíduo fino para o qual atualmente ainda não foi desenvolvida uma aplicação que possibilite a utilização em larga escala. Uma alternativa que vem sendo estudada é a associação com cimento Portland em composições de argamassas e concretos, em função da composição química do resíduo: elevada quantidade de alumínio, silício e magnésio, que podem apresentar interações com o ligante. No entanto, em função da elevada área superficial específica, em comparação ao cimento, sua utilização nas composições pode afetar a demanda de água de amassamento e limitar a sua aplicação. Para tanto, uma alternativa é a calcinação deste resíduo fino, assim como é realizado para outras argilas (caulim, por exemplo), para que a área superficial específica (ASE) seja menor e eventualmente ative propriedades pozolânicas na respectiva argila. Deste modo, neste trabalho foram avaliadas as diversas características de pastas cimentícias após adição de resíduo fino de vermiculita: reação química, formação dos produtos hidratados, propriedades reológicas, tanto após a mistura como ao longo da hidratação. Foi verificado que de forma geral a reação química não é afetada após a adição de vermiculita, embora a formação de aluminatos seja intensificada na composição com maior quantidade de resíduo in natura. Com relação ao seu comportamento no estado fresco, foi observado que a maior ASE do resíduo impacta fortemente as propriedades reológicas das pastas, embora que com um teor de 5% as mudanças sejam menores. Utilizando-se dessas mesmas composições para a avaliação do desempenho no estado endurecido de argamassas, foi verificado que não há efeito sobre essas propriedades até 5% de substituição, independentemente do tratamento térmico empregado. Assim, considerando aspectos econômicos de transporte assim como os custos decorrentes da calcinação, pode-se recomendar a adição de 5% de vermiculita in natura sem comprometer o desempenho dos produtos, embora não se possa precisar com os dados obtidos a sua durabilidade ao longo do uso. / In the process to obtaining vermiculite a fine residue is generated, which does not yet have a large-scale application. An alternative that has been studied is the association with Portland cement in mortar and concrete formulations, as a function of the chemical composition of the residue: high amount of aluminium, silicon and magnesium which may have interactions with the binder. However, the residue has a high specific surface area, in comparison to cement, a fact that can increase the water-demand to mix and limit its application. For this, an alternative is the calcination of this fine residue, as it is done for other clays (kaolin, for example), so that the specific surface area (SSA) is smaller and eventually activates pozzolanic properties in the respective clay. Thus, in this work the various characteristics of cement pastes after addition of vermiculite fine residue were evaluated: chemical reaction, formation of the hydrated products, rheological properties, both after mixing and along the hydration. It was verified that in general the chemical reaction is not affected after the addition of vermiculite, although the formation of aluminates is intensified in the composition with greater amount of in nature residue. Regarding its behaviour in the fresh state, it was observed that the higher SSA of the residue strongly impacts the rheological properties of the pastes, although with a 5% content the changes are minimal. Using these same compositions to evaluate the performance in the hardened state of mortars, it was verified that there is no effect on these properties up to 5% of substitution, regardless of the thermal treatment used. Thus, considering the economic aspects of transport as well as the costs of calcination, it is possible to recommend the addition of 5% of vermiculite in nature without compromising the performance of the products, although it is not possible to determine the its durability during the use.
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O uso de pozolanas como materiais cimentícios suplementares: disponibilidade, reatividade, demanda de água e indicadores ambientais. / Pozzolan as supplementary cementitious materials: avaiability, reactivity, water demand and environmental indicators.Abrão, Pedro Cesar Rodrigues Alves 07 December 2018 (has links)
O cimento está entre os materiais mais utilizados no mundo moderno e sua produção deverá crescer nos próximos 40 anos. Esta crescente produção será responsável pela emissão de um grande volume de CO2 na atmosfera, atualmente a indústria cimenteira é responsável mundialmente por 10% das emissões totais de CO2 e pode chegar a 30% em 2050. Portanto, a academia e a indústria estão desenvolvendo estratégias para reduzir este impacto ambiental, uma dessas estratégias é a substituição do clínquer por materiais cimentícios suplementares (MCSs). Para esta estratégia ser efetiva é necessário que estes materiais possuam: (i) viabilidade econômica; (ii) disponibilidade e; (iii) viabilidade técnica. Hoje os materiais suplementares mais utilizados são a escória de alto forno e a cinza volante, mas o aumento na produção do cimento não foi acompanhado pela oferta destes materiais. Assim, outros materiais suplementares estão sendo utilizados pela indústria, como é o caso das pozolanas naturais e artificiais. Portanto o objetivo deste trabalho é estimar a disponibilidade e distribuição geográfica de alguns materiais cimentícios suplementares no Brasil e avaliar a eficiência de seis cimentos pozolânicos comerciais e compará-los com um cimento com alto teor de clínquer quanto a reatividade, demanda de água e indicadores ambientais. Todos os materiais foram fisicamente e quimicamente caracterizados; pastas e argamassas foram analisadas em termos de reatividade, demanda de água e resistência mecânica; finalmente, foram estimados indicadores ambientais e de eficiência. Para pastas e argamassas sem dispersante o cimento com alto teor de clínquer e aqueles com adição de terra diatomácea demandaram mais água que os demais para um mesmo espalhamento, já com adição de superplastificante o cimento REF foi o que demandou mais água. O cimento com alto teor de clínquer foi o mais reativo em todas as idades e apresentou os melhores resultados do indicador de fração de água combinada e indicador de intensidade de ligante. Já para o indicador intensidade de carbono os melhores resultados foram obtidos para os cimentos com alto teor de substituição. No entanto, o estudo mostra que a redução do teor de clínquer não está diretamente relacionada à redução do impacto ambiental do cimento em seu uso, esta redução de impacto também está associada com a eficiência do ligante quanto a sua reatividade e demanda de água. / The cement is one of the most used materials in the modern world and its production should grow in the next 40 years. This growing production will be responsible for issuing a large volume of CO2 on the atmosphere, nowadays the cement industry is responsible worldwide for 10% of the total emissions of CO2 and it can reach 30% in 2050. Therefore, academia and industry are developing strategies to reduce this environmental impact, one of these strategies is the substitution of clinker by supplementary cementitious materials (SCMs). For this strategy to be effective it is necessary that these materials possess: (i) economic viability; (ii) availability and; (iii) technical feasibility. Today the most used supplementary materials are the blast furnace slag and fly ash, but the increase in the production of cement was not accompanied by the supply of these materials. Therefore, other supplementary materials are being used by the industry, as is the case of natural and artificial pozzolans. So, the aim of this work is to estimate the availability and geographic distribution of some supplementary cementitious materials in Brazil and evaluate the efficiency of six Portland pozzolan blended cements and compare them with a cement with high clinker content as to reactivity, water demand and environmental indicators. All materials were physically and chemically characterized; pastes and mortars were analyzed in terms of reactivity, water demand and mechanical strength; finally, environmental and efficiency indicators were estimated. For pastes and mortars without dispersant the cement with high content of clinker and those with the addition of diatomaceous earth ordered more water than the others to achieve the same spread, already with the addition of superplasticizer the cement REF was the one that ordered more water than the others. The cement with high clinker content was the most reactive in all ages and presented the best results of the binder efficiency indicator and binder intensity indicator. For the carbon intensity indicator, the best results were obtained for cements with high replacement content. However, the study shows that the reduction of the clinker content is not directly related to the reduction of the environmental impact of the cement in its use, this reduction is also associated with the binder efficiency in means of reactivity and water demand.
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