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Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2004. / Includes bibliographical references (leaves 168-186). Also available in electronic version. Access restricted to campus users.

Cement has been selected for wastes immobilization as a simple, low temperature and low cost process for decades. The mechanical and immobilization properties of cement are mainly decided by cement hydration process, especially in the first 24 hours. Previous methods for studying the cement hydration are those include isothermal calorimetry, continuous monitoring of chemical shrinkage, in situ quantitative X-ray diffraction, nuclear magnetic resonance spectroscopy (NMR), quasi-elastic neutron scattering (QENS) and small angle neutron scattering (SANS). Few available in-situ imaging methods were successfully used for net rate study of cement hydration. In this Ph.D. research, innovative imaging techniques such as X-ray computed tomography (XCT) combined with 2D SEM-BSD analysis were combined to study the microstructure and phase change of cement or cement & SrCl2 mixture during hydration. Digital Volume Correlation (DVC) and Digital Image Correlation (DIC) were applied to study the chemical volume shrinkageand drying shrinkage of cement samples during hydration. The effects of SrCl2 simulating the radioactive nuclide from nuclear waste on cement hydration were studied by XRD and ICP-AES techniques. These studies verified that the hydration net rate could be characterised by XCT imaging techniques and the volume shrinkage of cement or cement& SrCl2 mixture during hydration could be characterised by the DVC and DIC techniques.

Thesis (Ph. D.)--University of Texas at El Paso, 2008. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Estimating the delayed strains in concrete, namely creep and shrinkage is very important to asses the condition of the structure. Time dependent deformations in concrete, both creep and shrinkage, play a critical role in prestressed concrete structures, such as bridge girders, nuclear containment vessels, etc. These strains result in lossess, through release of prestress, and thereby influence the safety of these structures. Recognizing the role of free and bound moisture movement is the primary ingredient responsible for the development of both creep and shrinkage stains as well as the degradation of concrete under high temperature, the present study has also examined the effects of high temperature on concrete degradation, experimentally and also analytically in the same modelling framework. Fire in concretes deteriorates mechanical properties of the material and lead to col-lapse under loads. Two types of spalling occur in concrete when exposed to high temperature, namely explosive and thermal spalling. Explosive spalling occurs once the hydrostatic stress (developed due to pore pressure) exceeds the tensile strength of the concrete. Where as thermal spalling of concrete happens due to degradation of material properties (elastic modulus, compressive and tensile strength) when exposed to high temperature due to decomposition of chemical bonds that release the bound water. The present study comprises of an experimental and analytical program to assess the levels of creep and shrinkage in different concrete under various loads and environmental conditions. Deformations due to high temperature in di erent concretes forms another component of the present study. Total six concrete mixes has been studied to investigate and asses the extent of creep and shrinkage taking place in the concretes under different environmental conditions, load level and age at loading. In total six mixes, three that are self compacted concrete mixes (35MPa, 55MPa and SCC70MPa), a high volume y ash concrete mix ( 45 MPa) and two normal concrete mixes (35 MPa and 45 MPa) have been considered in this study. To study the high temperature effects, the same mixes considered in the creep and shrinkage study and in addition a heavy density concrete mix (25 MPa) is used. A normal concrete having a 28 day uniaxial compressive strength of 45 MPa after proper curing, referred to as M45 concrete, was one of the six mixes. Likewise a heavy density concrete designated as H25, corresponding to a 28 day uniaxial compressive strength of 25 MPa was another mix that was studied and was made using iron ore aggregate and iron ore sand. A concrete having high volume y ash replacing cement designated as F45 offered a 28 day strength of 45MPa. Three self-compacting concretes with uniaxial compressive strengths of 35, 55 and 70 MPa were designated as SCC35 SCC55 and SCC70, respectively is studied for creep, shrinkage and high temperature effects. F45 concrete shows lower creep strain when compared to normal M45 concrete, under similar casting, curing and testing condtions. This is due to increase in stiffness of y ash based concretes with time. Where as in shrinkage it is observed that a little higher strain takes place in F45 at initial ages than in M45 concrete mix for the same conditions. But in the later age, F45 concrete shows a decreasing rate of shrinkage strain. This is because, water to cement ratio of y ash concrete is higher than the M45 concrete. The SCC35 concrete shows higher creep and shrinkage than M35 concrete even though both the concretes have the same water cement ratio. This difference comes from the aggregate cement ratio (a/c). The lower the aggregate cement ratio, the higher the creep and shrinkage. M35 concrete has a higher aggregate cement ratio than the SCC35. Concretes exposed to higher temperature and lower humidity shows higher creep and shrinkage due to its higher rate of drying. An analytical model has been developed to simulate the drying phenomena in concrete based on poromechanics. The hydration effects of blended cements is considered while developing the model. This models prediction of degree of hydration, temperature and relative humidity is used to model creep and shrinkage in concrete. To model creep and shrinkage, micro prestress solidi cation theory is implemented and validated with the present experimental results. The model is able to predict the drying phenomena of concrete realistically. Further, a benchmark problem reported in the literature is solved through this model and validated through a comparison with the experimental results (beam detection due to creep and shrinkage). Under high temperature tests, H25 concrete shows better resistance for all the ranges of temperatures. This may be because of the hematite aggregate having a high melting point and strong interfacial transition zone (ITZ) properties between aggregate and cement mortar. The SCC70 shows poor performance against explosive spalling at both the ages (28 and 365 days) due to its lower permeability when exposed to high temperature. The intensity of explosive spalling is higher in SCC70 concrete tested at 28 days than at 365 days of age. This is because of variation in moisture content. SCC70 concrete failed due to explosive spalling at temperature of 398oC when tested at 28 days and failed at 575oC when tested at 365 days. This indicates the amount of moisture content in the concrete plays an important role while causing explosive spalling. F45 concrete shows a poor resistance against temperature beyond 500oC in its residual properties. SCC55 contains cement and y ash and shows higher residual properties when compared to normal vibrated M45 mix under similar high temperature conditions. Two geopolymers pastes prepared with y ash and metakaolin as a complete cement replacement were studied for passive re protection capability. The study shows MF70 mix (containing 70% y ash and 30% metakaolin) gives better resistance against heating than MF50 mix (50% each of metakaolin and y ash). Hence y ash geopolmer is a choice of material for passive re protection. An analytical model has been developed based on poromechanics to simulate high temperature e ects in concrete. Two type of spalling is considered while modelling the high temperature e ects of concrete, namely explosive and thermal spalling. Explosive spalling is estimated based on the hydro static stress (Biotech efficient times the pore pressure). If the hydrostatic stress increases beyond the tensile strength of concrete then explosive spalling occurs. Where as the thermal spalling is estimated based on the stresses developed due to applied mechanical and thermal loading. To validate this model, two benchmark problems from the literature have been solved and validated with the reported results. This model is able to predict pore pressure and temperatures gradients accurately, and this in turn helps to predict explosive and thermal spalling realistically in concrete under elevated temperature conditions.

Dada a considerável parcela de responsabilidade da indústria de produção de cimento no total de emissão mundial de CO2, um dos desafios atuais mais importantes é a adoção de estratégias que reduzam a utilização do cimento, sem prejuízo ao desempenho mecânico e a durabilidade dos materiais cimentícios. Dentre essas estratégias, uma das usualmente empregadas em alguns segmentos industriais é a reutilização de ligante pré-hidratado na produção. O entendimento de como a pré-hidratação altera as propriedades de pastas cimentícias tem também importante implicação científicas, quanto à cinética de reação do cimento Portland, mas sobretudo devido aos impactos nas propriedades reológicas da pasta, tanto após a mistura quanto ao decorrer da hidratação. Sabe-se que a pré-hidratação altera a cinética de hidratação do cimento, impactando as suas propriedades no estado endurecido. Além disso, a pré-hidratação modifica as propriedades físicas do cimento, influenciando diretamente no modo como as partículas se aglomeram. No entanto, boa parte da literatura refere-se à pré-hidratação que ocorre após má estocagem, diferentemente deste trabalho que trata da pré-hidratação em suspensão, mais comum em processos industriais. Assim, neste trabalho foi avaliada a cinética de reação por calorimetria isotérmica enquanto as propriedades reológicas foram avaliadas por reometria rotacional e oscilatória. Para a identificação e quantificação dos hidratos formados, a hidratação foi paralisada e foram realizados testes de TG e DRX. Os resultados mostraram que a adição do pré-hidratado altera a cinética de dissolução/precipitação do cimento anidro. Assim, quanto maior o teor de pré-hidratado e o período de pré-hidratação, menor o tempo de indução, antecipando a formação dos hidratos (silicatos e aluminatos), embora a taxa de reação no período de aceleração não tenha sido afetada de forma significativa. Quanto às propriedades físicas das partículas, forma realizados teste de granulometria, ASE (Área Superficial Específica) e densidade real. A pré-hidratação aumenta a sua ASE, o que acarreta no incremento da tensão de escoamento e da viscosidade das pastas. Inclusive, se esse aumento de ASE for incorporado em determinados modelos (YODEL e Interferência) é possível a predição dessas propriedades reológicas. O aumento de ASE também é responsável pelo maior enrijecimento e menor tempo de pega das suspensões pré-hidratadas. Correlacionando a reação química com a consolidação da pasta, ficou demonstrado que o maior enrijecimento da pasta pré-hidratada tem relação com a maior aproximação entre as partículas, a ASE inicial das pastas e a reatividade do pré-hidratado, otimizando assim a formação da microestrutura pela hidratação. / Given the considerable share of cement industry on overall share of CO2 emissions, one of the most important current challenges is the adoption of strategies that reduce the use of cement without compromising the mechanical performance and durability of cementitious materials. Among these strategies, one of the commonly employed in some industrial segments is the reuse of pre-hydrated binder in production. The understanding of as pre-hydration changes the properties of cementitious pastes also has important scientific implication regarding the reaction kinetics of Portland cement, but mainly due to the impacts on the rheological properties of the paste, both after mixing and along hydration. It is known that pre-hydration alters the hydration kinetics of the cement, impacting its properties in the hardened state. In addition, pre-hydration modifies the physical properties of the cement, directly influencing the way as the particles agglomerates. However, much of the literature refers to the pre-hydration that occurs after bad storage, unlike this work that works with pre-hydration in suspension, more common in industrial applications. Thus, in this work the kinetics of reaction by isothermal calorimetry was evaluated while the rheological properties were evaluated by rotational and oscillatory rheometry. For the identification and quantification of the hydrates formed, the hydration was paralyzed and TG and XRD tests were performed. The results showed that the inclusion of the pre-hydrate alters the dissolution/precipitation kinetics of the anhydrous cement. Thus, the higher the pre-hydration content and the pre-hydration period, the shorter the induction time, anticipating the formation of the hydrates (silicates and aluminates), although the reaction rate in the acceleration period was not significantly affected. As for the physical properties of the particles, there were realized tests of particle size distribution, SSA (Specific Surface Area) and real density. The pre-hydration increases its SSA, which leads to an increase in the yield stress and viscosity of the pastes. Even if this increase of SSA is incorporated in certain models (YODEL and Interference) it is possible to predict these rheological properties. The increase in ASE is also responsible for the greater hardening and quickly setting time of the pre-hydrated suspensions. Correlating the chemical reaction with paste consolidation, it was demonstrated that the higher hardening of the pre-hydrated paste is related to the greater approximation between the particles, the initial ASE of the pastes and the reactivity of the pre-hydrate, optimizing then the formation of the microstructure by hydration.

Dada a considerável parcela de responsabilidade da indústria de produção de cimento no total de emissão mundial de CO2, um dos desafios atuais mais importantes é a adoção de estratégias que reduzam a utilização do cimento, sem prejuízo ao desempenho mecânico e a durabilidade dos materiais cimentícios. Dentre essas estratégias, uma das usualmente empregadas em alguns segmentos industriais é a reutilização de ligante pré-hidratado na produção. O entendimento de como a pré-hidratação altera as propriedades de pastas cimentícias tem também importante implicação científicas, quanto à cinética de reação do cimento Portland, mas sobretudo devido aos impactos nas propriedades reológicas da pasta, tanto após a mistura quanto ao decorrer da hidratação. Sabe-se que a pré-hidratação altera a cinética de hidratação do cimento, impactando as suas propriedades no estado endurecido. Além disso, a pré-hidratação modifica as propriedades físicas do cimento, influenciando diretamente no modo como as partículas se aglomeram. No entanto, boa parte da literatura refere-se à pré-hidratação que ocorre após má estocagem, diferentemente deste trabalho que trata da pré-hidratação em suspensão, mais comum em processos industriais. Assim, neste trabalho foi avaliada a cinética de reação por calorimetria isotérmica enquanto as propriedades reológicas foram avaliadas por reometria rotacional e oscilatória. Para a identificação e quantificação dos hidratos formados, a hidratação foi paralisada e foram realizados testes de TG e DRX. Os resultados mostraram que a adição do pré-hidratado altera a cinética de dissolução/precipitação do cimento anidro. Assim, quanto maior o teor de pré-hidratado e o período de pré-hidratação, menor o tempo de indução, antecipando a formação dos hidratos (silicatos e aluminatos), embora a taxa de reação no período de aceleração não tenha sido afetada de forma significativa. Quanto às propriedades físicas das partículas, forma realizados teste de granulometria, ASE (Área Superficial Específica) e densidade real. A pré-hidratação aumenta a sua ASE, o que acarreta no incremento da tensão de escoamento e da viscosidade das pastas. Inclusive, se esse aumento de ASE for incorporado em determinados modelos (YODEL e Interferência) é possível a predição dessas propriedades reológicas. O aumento de ASE também é responsável pelo maior enrijecimento e menor tempo de pega das suspensões pré-hidratadas. Correlacionando a reação química com a consolidação da pasta, ficou demonstrado que o maior enrijecimento da pasta pré-hidratada tem relação com a maior aproximação entre as partículas, a ASE inicial das pastas e a reatividade do pré-hidratado, otimizando assim a formação da microestrutura pela hidratação. / Given the considerable share of cement industry on overall share of CO2 emissions, one of the most important current challenges is the adoption of strategies that reduce the use of cement without compromising the mechanical performance and durability of cementitious materials. Among these strategies, one of the commonly employed in some industrial segments is the reuse of pre-hydrated binder in production. The understanding of as pre-hydration changes the properties of cementitious pastes also has important scientific implication regarding the reaction kinetics of Portland cement, but mainly due to the impacts on the rheological properties of the paste, both after mixing and along hydration. It is known that pre-hydration alters the hydration kinetics of the cement, impacting its properties in the hardened state. In addition, pre-hydration modifies the physical properties of the cement, directly influencing the way as the particles agglomerates. However, much of the literature refers to the pre-hydration that occurs after bad storage, unlike this work that works with pre-hydration in suspension, more common in industrial applications. Thus, in this work the kinetics of reaction by isothermal calorimetry was evaluated while the rheological properties were evaluated by rotational and oscillatory rheometry. For the identification and quantification of the hydrates formed, the hydration was paralyzed and TG and XRD tests were performed. The results showed that the inclusion of the pre-hydrate alters the dissolution/precipitation kinetics of the anhydrous cement. Thus, the higher the pre-hydration content and the pre-hydration period, the shorter the induction time, anticipating the formation of the hydrates (silicates and aluminates), although the reaction rate in the acceleration period was not significantly affected. As for the physical properties of the particles, there were realized tests of particle size distribution, SSA (Specific Surface Area) and real density. The pre-hydration increases its SSA, which leads to an increase in the yield stress and viscosity of the pastes. Even if this increase of SSA is incorporated in certain models (YODEL and Interference) it is possible to predict these rheological properties. The increase in ASE is also responsible for the greater hardening and quickly setting time of the pre-hydrated suspensions. Correlating the chemical reaction with paste consolidation, it was demonstrated that the higher hardening of the pre-hydrated paste is related to the greater approximation between the particles, the initial ASE of the pastes and the reactivity of the pre-hydrate, optimizing then the formation of the microstructure by hydration.

L’ajout d’adjuvants dans les mortiers permet d’obtenir diverses propriétés selon lesperformances souhaitées. Les polysaccharides sont utilisés pour améliorer la capacité derétention d’eau et le comportement rhéologique du mortier. Cependant, ils engendrent unretard de prise du ciment et représentent un poids économique considérable. Il apparaît doncque la compréhension de l’interaction entre les polysaccharides et le ciment est nécessaire.Etant donné que les comportements sont différents selon le type de polysaccharide, l’étuded’une nouvelle famille de polysaccharides constitue un axe de recherche majeur. Leshydroxypropylguars (HPG) ont été choisis car ils ont été présentés comme de très bonsagents rétenteurs d’eau et sont déjà utilisés industriellement.Il s’avère que les HPG confèrent effectivement aux mortiers d’excellentes propriétés derétention d’eau. Le mécanisme de rétention d’eau est attribué à la formation d’agglomératsqui, au-delà d’une concentration critique, bouchent le réseau poreux à l’interface mortier-substrat.De plus, ces molécules ralentissent nettement la cinétique d’hydratation du cimenten modifiant la croissance des hydrates par adsorption. Les HPG augmentent également la contrainte seuil de cisaillement et la consistance des mortiers. Toutes cespropriétés diffèrent lorsque les HPG sont introduits pré-dissout dans l’eau de gâchée. Uneméthodologie de fragmentation par ultra-sons des polysaccharides a été développée dans lebut d’étudier l’impact de leur masse moléculaire sur les propriétés des mortiers à l’état frais.Sur tous ces aspects, le comportement des HPG a été comparé à celui des éthers de cellulose,adjuvants rétenteur d’eau de référence. / Modern factory-made mortars are complex materials, in which are added some kinds of admixtures used to exhibit various properties. Polysaccharides are admixtures used in order to improve water retention capacity and rheological behavior of freshly-mixed mortars.However, polysaccharides induce a delay of cement hydration and represent a large part of mortar raw material cost. The improvement of the knowledge about polysaccharide-cement interaction is therefore necessary. In past, different behaviors were observed according to the kind of polysaccharide. The study of a new polysaccharide family is thus a major way of research. The hydroxypropylguars were chosen since they were presented as promising water retention agents and they are now well-established in the construction industry.Results show that HPG improve the water retention capacity of cement-based mortars. The working mechanism is attributed to the formation of HPG aggregates above a critical dosage, which may stop the water flow by plugging the porous network at the interface mortar-substrate. Moreover, HPG induce a decrease in the hydrates growth rate because of adsorption on the cement hydrated phases, and enhance the consistency and the yield stress of mortars. All these properties are influenced by the pre-dissolution of HPG in the mixing water. A methodology of ultrasonic degradation was also established in order to study the molecular weight influence of polysaccharides on fresh-state properties. Cellulose ethers were systematically investigated as polysaccharidic admixture reference.

Student Number : 9900772K - MSc research project - School of Civil and Environmental Engineering - Faculty of Engineering and the Built Environment / The hydration of cement is an exothermic reaction, which begins almost immediately upon contact with water. This produces a large amount heat that subsequently raises the temperature of the concrete mixture, creating a temperature gradient across the member. The temperature rise associated with hydration induces thermo-mechanical stresses. These stresses can cause damage to the structure, affecting the durability and in extreme cases the functionality of the structure. If the maximum rate of heat evolution experienced can be minimised through the selection of the constituents of a concrete mixture, then the thermal stresses that develop in the concrete can be reduced. The main aim of this research is to develop a knowledge of how the heat evolution characteristics of concrete are affected by changing certain concrete mixture parameters and ingredients. The focus is on the addition of three different cement extenders and varying the water/cement ratio. This will be a step towards the development of a model for predicting the thermal properties of concrete. As a part of this investigation, a prediction model for the change in heat rate in concrete was developed. The model is intended to predict the contribution of the individual clinker crystallographic phases in cement and the heat liberated in concrete during hydration.

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.