O metacaulim é um material pozolânico que vem sendo pesquisado e adotado em vários países. O metacaulim é constituído basicamente de sílica (SiO) e alumina (Al2O3) na fase amorfa, capaz de reagir com o hidróxido de cálcio Ca(OH) gerado durante a hidratação do cimento Portland, formando produtos hidratados similares aos decorrentes da hidratação direta do clinquer Portland. Esta pozolana acelera o processo de hidratação do cimento, formando silicato de cálcio hidratado (C-S-H) adicional. O conhecimento das características do metacaulim que influenciam a interação com a cal, se faz necessário para subsidiar medidas preventivas com relação ao consumo de portlandita. O presente trabalho visa determinar as características físico-químicas relevantes para o entendimento da atividade pozolânica, avaliando as reações propiciadas pelo metacaulim em sistemas binários. Para este propósito, realizaram-se estudos experimentais em pasta e concreto, usando as técnicas de difratometria de raios X e de termogravimetria. As etapas experimentais consistiram: na caracterização do metacaulim, com ênfase na determinação do teor da fase amorfa; a avaliação da cinética da reação em sistema metacaulim/hidróxido de cálcio e análise da evolução da hidratação de cimento com alto teor de metacaulim. Nos sistemas cimenticios de concretos com diferentes teores de substituição de metacaulim com e sem cal hidratada, foi avaliado o comportamento da resistência à compressão. No metacaulim estudado, o teor da fase amorfa foi de 74,60% e o restante (25,40%) atua como material inerte, e o consumo máximo por atividade pozolânica, foi de 1,34 gr de Ca(OH)/grama de fase amorfa de metacaulim. Na evolução das reações, por atividade pozolânica o C-S-H foi formando gradativamente. A adição de 15% de metacaulim e 5% de cal hidratada em concretos proporcionou um ganho de resistência de 17% a mais em função do concreto de referência. / The metakaolin is a pozzolanic material that has been investigated and adopted in several countries. The metakaolin consists primarily of silica (SiO) and alumina (Al2O3) in the amorphous phase, and can react with calcium hydroxide Ca (OH) generated during hydration of Portland cement to form products similar to those obtained during Portland clinker basic hydration. This pozzolana could accelerate the hydration of cement, forming calcium silicate hydrate (C-S-H) additional. The knowledge of the characteristics of metakaolin that influence the interaction with lime provides the necessary subsidize to prevent excessive consumption of portlandite. This paper aims to determine the physical and chemical relevant characteristics in order to understand the pozzolanic activity, evaluating the responses provided by the metakaolin in binary systems. For this purpose, experimental studies were conducted in paste and concrete, using the techniques of X-ray diffraction and thermogravimetry. The experimental steps consisted of: the characterization of metakaolin, with emphasis on determining the amorphous phase content, this evaluation of the kinetics of the reaction system metakaolin and calcium hydroxide; The analysis of the evolution of the cement hydration with high content of metakaolin. In cementitious systems of concrete with different metakaolin replacement levels with and without hydrated lime, was rated the behavior of the compressive strength. The content of amorphous phase In the studied metakaolim was 74.60% and the remainder (25.40%) acts as an inert material, and the máximum consumption by pozzolanic activity was 1.34 g of Ca (OH)/g amorphous phase of metakaolin. During the evolution of pozzolanic reactions, the C-S-H was gradually formed. The addition of 15% metakaolin and 5% hydrated lime in concrete has a strength gain of 17% more depending on the reference concrete.

The influence of supplementary materials such as slag, metakaolin and limestone in steam-cured ternary and quaternary cement blends on physical and chemical hydration mechanisms was studied by analyzing the evolution of non-evaporable water content, hydration products and compressive strength. The role of limestone in hydration reactions of cement was also investigated. These properties were studied through the use of differential thermal and thermogravimetric analyses, as well as the loss-on-ignition, X-ray diffraction and compressive strength tests at 1, 3, 7, and 28 days. Research findings revealed that it is possible to replace up to 40% cement with other materials and still achieve compressive strengths similar to mixtures with a 25% cement replacement at 0.34 w/b ratio. Additionally, ternary limestone mixtures exhibited superior mechanical properties to ternary metakaolin mixtures. Lastly, limestone powder was determined to behave as inert filler, accelerating hydration at early ages through heterogeneous nucleation.

The influence of supplementary materials such as slag, metakaolin and limestone in steam-cured ternary and quaternary cement blends on physical and chemical hydration mechanisms was studied by analyzing the evolution of non-evaporable water content, hydration products and compressive strength. The role of limestone in hydration reactions of cement was also investigated. These properties were studied through the use of differential thermal and thermogravimetric analyses, as well as the loss-on-ignition, X-ray diffraction and compressive strength tests at 1, 3, 7, and 28 days. Research findings revealed that it is possible to replace up to 40% cement with other materials and still achieve compressive strengths similar to mixtures with a 25% cement replacement at 0.34 w/b ratio. Additionally, ternary limestone mixtures exhibited superior mechanical properties to ternary metakaolin mixtures. Lastly, limestone powder was determined to behave as inert filler, accelerating hydration at early ages through heterogeneous nucleation.

Two metakaolins were evaluated for use as supplementary cementitious materials in cement-based systems. The metakaolins varied in their surface area (11.1 v. 25.4 m2/g), but were quite similar in mineralogical composition. Performance of metakaolin mixtures was compared to control mixtures and to mixtures incorporating silica fume as partial replacement for cement at water-to-cementitious materials ratios of 0.40, 0.50, and 0.60. In this study, the early age properties of fresh concrete and the mechanical and durability properties of hardened concrete were examined. Early age evaluations aimed to determine the reactivity of metakaolin (heat of hydration) and its effect on mixture workability (slump, setting time, unit weight). In addition, three types of shrinkage were monitored in metakaolin-cement systems: chemical, autogenous, and free. Compressive, tensile, and flexural strength and elastic modulus were measured at various concrete ages. The influence of metakaolin addition on durability was assessed through accelerated testing for sulfate resistance, expansion due to alkali-silica reaction, and through rapid chloride permeability measurements. To further quantify the underlying mechanisms of metakaolin's action, the microstructure of pastes was examined. Calcium hydroxide (CH) content was determined using thermogravimetric analysis and verified using differential thermal analysis. Surface area and pore size distribution were evaluated via nitrogen adsorption. These analyses yielded information about the pozzolanic reactivity of metakaolin, associated CH consumption and pore structure refinement, and resulting improvements in mechanical performance and durability of metakaolin-concretes.

Geopolymers (GPs) are a new class of inorganic polymers that have been considered as good candidate materials for many applications, including fire resistant and refractory panels, adhesives, and coatings, waste encapsulation material, etc. The aim of this study is to establish relationship between structural and mechanical properties of geopolymers with different chemical compositions. The metakaolin-based geopolymers were prepared by mechanically mixing metakaolin and alkaline silicate aqueous solutions to obtain samples with SiO2/Al2O3 molar ratio that ranges from 2.5 to 5, and Na/Al or K/Al atomic ratios equal to 1. Geopolymer samples were cured in a laboratory oven at 80°C and ambient pressure for different times in the sealed containers. Structural characterization of the samples with different chemical compositions was carried out using X-Ray Diffraction (XRD), Fourier Transform Infrared (FTIR) spectroscopy, Nuclear Magnetic-Resonance (NMR) spectroscopy and Scanning Electron Microscopy (SEM) with Energy Dispersive Spectroscopy (EDS). The mechanical characterization included Micro-indentation, Vickers indentation and fracture toughness measurement, as well as compressive testing. It was found that structure and mechanical properties of GPs depend on their chemical composition. The Na-GPs with ratio 3 have a highest compressive strength and Young‘s modulus of 39 MPa and 7.9 GPa, respectively. The results of mechanical testing are discussed in more detail in this thesis and linked to structural properties of processed geopolymers.

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

Geopolymers are a relatively new class of material that has many broad applications, including use as a substitute for Ordinary Portland Cement (OPC), use in soil stabilisation, fire resistant panels, refractory cements, and inorganic adhesives. The synthetic alkali aluminosilicate structure of geopolymer results in a highly versatile material that can be synthesised en masse, cost competitively and from a wide varietyof aluminosilicate bearing raw materials. / Despite the commercial promise and technical viability of the technology, the fundamental understanding of the chemical structure and characteristics of geopolymeric materials, and to some degree the academic rigor of some aspects of the science related to geopolymers, leave a lot to be desired. In particular, the understanding of the effects of Si/Al ratio and alkali cation type on the molecular structure of the binder, and how these relate to the microstructure and mechanical and thermal properties are poorly understood. / The thesis explores the structure and characteristics of a systematic multi-dimensional matrix of geopolymers derived from metakaolin, a relatively pure aluminosilicate source. The thesis addresses the determination of the core molecular structure of geopolymers by solid-state NMR spectroscopy, and how this is altered by the nominal Si/Al ratio and alkali cation type. The chemical ordering is observed to reduce with Si/Al ratio and with inclusion of potassium over sodium. Most significantly, the presence of Al-O-Al linkages is identified for the first time in specimens with Si/Al ratios close to unity, by the application of 17O NMR techniques on geopolymers. The role of molecular structure and gel chemistry of geopolymers is elucidated, and links are drawn to understand the development of the microstructure and physical properties of the material. The thermal evolution of geopolymeric gels derived from metakaolin is investigated in terms of physical and structural development when exposed to temperatures up to 1000°C. The response of geopolymers to heating is characterised into four regions regardless of the extent of shrinkage or crystallisation. Several critical material performance relationships exist that are related to both the microstructure and chemical composition. / The thesis presents an updated structural model of geopolymers to include new insights obtained from application of solid-state NMR techniques and thermal analysis. The improvements in structural understanding described in the thesis have the potential to affect all aspects of geopolymer science.

Orientador: Mauro Mitsuuchi Tashima / Resumo: A constante preocupação com o meio ambiente, principalmente, em relação à emissão de gases de efeito estufa na atmosfera, é uma das grandes razões pelas quais pesquisadores buscam por aglomerantes alternativos ao cimento Portland. Associado a este fato, está também a geração e o manejo dos resíduos sólidos urbano e industriais. Neste sentindo, os aglomerantes ativados alcalinamente têm sido apontados como “os novos cimentos do futuro”, uma vez que proporcionam uma redução na emissão CO2 pelo menor consumo de cimento Portland e pelo potencial de absorção dos resíduos, já que estes tem sido muito empregado como precursores na produção dos aglomerantes ativados alcalinamente, além de apresentarem melhores propriedades que o cimento Portland. Diante disto, o objetivo desta pesquisa foi avaliar a viabilidade e os efeitos da utilização da cinza de lodo de esgoto (CLE) em geopolímeros à base de metacaulim. Sistemas binários compostos por metacaulim (MK) e CLE foram confeccionados e submetidos a diferentes condições de cura – temperatura ambiente (25°C) e banho térmico (65°C) usando como solução alcalina a mistura de NaOH e uma solução de silicato de sódio. A CLE foi empregada como substituição parcial do MK em proporções de 0-20%. As amostras foram avaliadas por difração de raios – X, microscopia eletrônica de varredura e por resistência à compressão. Os resultados mostraram a formação de zeólitas (Faujasita) nas amostras curadas em banho térmico, que provocou uma redução de até 16,... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre

The aim of the project is to utilise fly ash (PFA), a waste material/industrial byproduct, with metakaolin (MK), as a partial replacement for Portland cement (PC) in mortar and paste. The influence of various compositions of MK-PFA-PC blends on the resistance to the action of sulphate and synthetic seawater solutions, setting time and heat of hydration will be examined. MK is calcinated clay and is a relatively new pozzolanic material. Although it is a very effective pozzolan it is also very expensive. Using FA, which is a much less expensive material, as a PC replacement material, is problematic, as there is slow and low early strength development whereas MK enhances early strength development. Combining these materials in ternary blends should therefore produce a high performance material at an acceptable cost for use as a pozzolan. However the properties and performance of such a material still need to be fully established. The results of the research show, for the initial and final setting time of binary MK-PC pastes there is a substantial increase at 5% MK and then decreases at 10 and 15% MK before increasing again at 20% MK replacement level. However, with PFA there are different trends to those observed when using MK alone. The initial and final setting time of binary PFA-PC pastes shows a slight increase at 10% PFA and then systematically increases with increase in PFA content up to 40% PFA. Evaluation of sample preparation for porosimetry found that, overall, the compression tested samples show a lower proportion of 'fine pores' (volume (%) 0.05) jam than the cored and cut paste disks. It is deducted that this is due to the widespread microcracking during failure of the cubes under compressive loading thus modifying the pore structure present in the compressive tested samples. In strength development of mortar there is very little advantage in using MK over binary PFA-PC mortar blends when exposed to sulphate solution for up to 2 years. The strength behaviour in seawater is however quite different from that observed in mortar exposed to sulphate solution. As the MK replacement levels increase relative to the PFA levels the resistance to seawater attack improves significantly. In mortar exposed to sulphate solution the durability is greatly improved at high replacement levels in both binary and ternary blends. The durability of mortar exposed to seawater is greatly improved at 30 and 40% total replacement in ternary blended mortars.

Les principaux objectifs de cette thèse étaient d'évaluer la formulation et la durabilité des géopolymères à base de métakaolin utilisés comme liants dans des matériaux de construction. Les géopolymères sont des matériaux à activation alcaline faisant l'objet d'études de plus en plus nombreuses de la communauté internationale car ils représentent une alternative aux ciments Portland traditionnels. La première partie de cette étude a donc été dédiée à la formulation de ces matériaux réalisés exclusivement à partir de métakaolin flash et de silicate de sodium et a permis de mettre en évidence des performances comparables à un CEM I 52.5. Une caractérisation physico-chimique ainsi qu'une étude du réseau poreux a souligné les différences entre ces deux matériaux et a permis l'élaboration d'une base de donnée sur les caractéristiques du matériau. La réalisation de béton, allant jusqu'à la fabrication en usine de préfabrication, a montré la capacité des géopolymères à remplacer totalement les liants hydrauliques connus, en terme de mise en œuvre et de performances mécaniques. Les questions de durabilité liées au fort taux d'alcalins dans cette matrice ont été traitées par des études sur la réaction alcali-silice et sur la carbonatation. Les résultats obtenus ont permis de conclure que la réaction alcali-silice ne serait pas préjudiciable dans une matrice de métakaolin activé par du silicate de sodium, et que la réaction très rapide des alcalins de la solution interstitielle des pâtes de géopolymère avec le CO2 atmosphérique ne conduirait pas à une chute de pH significative, préjudiciable dans les matrices cimentaires, mais faciliterait l'apparition d'efflorescences. / The main objectives of this thesis were to assess the formulation and durability of metakaolin-based geopolymers as a binder for civil engineering materials. Geopolymers are alkali-activated materials; they are increasingly studied by the international community as they represent an alternative to traditional Portland cement. The first part of this study has been dedicated to the formulation of these materials, exclusively made from flash metakaolin and sodium silicate, which has shown performances comparable to a CEM I 52.5. A physicochemical characterization and a study of the porous network have highlighted differences between these two materials and allowed developing a database on the characteristics of the material. The achievement of concrete, up to precast plant, showed their ability to completely substitute known hydraulic binders, in terms of workability and compressive strength. Durability issues related to the high alkali content in this matrix were assessed by studies on alkali-silica reaction and carbonation. The results obtained have concluded that the alkali-silica reaction would not be detrimental in a matrix of metakaolin activated by sodium silicate, and that the very rapid reaction of the alkalis in the geopolymer pastes pore solution with atmospheric CO2 do not lead to a significant drop of the concrete pH, which could be detrimental in cement matrix, but could lead to the appearance of efflorescence on the surfaces of geopolymer.