O presente trabalho tem por objetivo investigar e propor uma metodologia rápida e eficaz de avaliação da reatividade do cimento Portland frente ao ataque por sulfatos. O método consiste na utilização de amostras de pasta de cimento hidratada em pó, colocadas em contato direto com soluções concentradas de Na2SO4 e MgSO4, em temperatura elevada (65ºC), para acelerar o ataque. Apesar dos cimentos estudados possuírem composição química parecida, os resultados de SO3 combinado mostraram que o cimento Classe G foi pouco menos suscetível ao ataque por sulfatos em função do maior teor de Fe2O3 presente. Da TG e DRX observou-se a formação de etringita no ataque por ambos os sais de sulfato; e formação de gipsita no ataque por MgSO4. Enquanto havia disponibilidade de portlandita na pasta hidratada, o cimento com adição mineral incorporada apresentou mesma taxa de ataque que os demais (sem adição), entretanto a partir do momento que toda a portlandita foi consumida, iniciou-se um processo de descalcificação do C-S-H, observado pela DRX. / The main point of this research is to propose a fast and effective method of evaluation of the cement reactivity to sulfate attack. Resistance to sulfate attack was measured by determining the combined sulfate in cement paste samples with exposure to Na2SO4 and MgSO4 solution, at high temperature (65°C). The samples of cement paste was triturated (powdered) in the proposed method. The results of combined SO3 showed that the Class G cement was little less susceptible to the sulfate attack because it has larger amount of Fe2O3. The ettringite formation was observed in the attack for both sulfate salts; and gypsum formation in the attack for MgSO4 (results of TG and XRD). The blended cement presented same results that the others, however when the Ca(OH)2 was totally consumed, it observed the decalcification of the C-S-H, by XRD.

In this research, two phases of work were conducted. First, an investigation into the durability concerns for precast prestressed concrete piles exposed to marine environments was conducted. The investigation characterized the durability concerns of chemical, biological, and physical deterioration mechanisms. The results of this study were used to develop potential high performance marine concretes (HPMC) that would be capable of 100+ year service lives in marine environments. Extensive durability testing and service life modeling of the HPMC was performed. Chloride ingress resistance was investigated using accelerated and long-term test procedures and the results used to perform service life modeling to predict the time before corrosion initiation. Sulfate resistance characterization was performed using multiple techniques to characterize the physical and chemical behavior of binder compositions containing binary or ternary mixes containing cement and supplementary cementitious materials (SCM's) subjected to a sulfate-laden environment. Accelerated carbonation testing and material characterization led to the finding of relationships in the chemical composition of mix designs and the observed durability and the results used to perform corrosion initiation service life modeling. An investigation into the influence of self-healing of cracked concrete led to fundamental findings on the behavior of chloride ingress for cracked concrete structures in marine environments. The results of this research led to the development of concrete mix designs capable of providing service lives over 100 years in Georgia's marine environments, as well as the advancement of the current state of knowledge on the durability characteristics of ternary mix designs.

O presente trabalho tem por objetivo investigar e propor uma metodologia rápida e eficaz de avaliação da reatividade do cimento Portland frente ao ataque por sulfatos. O método consiste na utilização de amostras de pasta de cimento hidratada em pó, colocadas em contato direto com soluções concentradas de Na2SO4 e MgSO4, em temperatura elevada (65ºC), para acelerar o ataque. Apesar dos cimentos estudados possuírem composição química parecida, os resultados de SO3 combinado mostraram que o cimento Classe G foi pouco menos suscetível ao ataque por sulfatos em função do maior teor de Fe2O3 presente. Da TG e DRX observou-se a formação de etringita no ataque por ambos os sais de sulfato; e formação de gipsita no ataque por MgSO4. Enquanto havia disponibilidade de portlandita na pasta hidratada, o cimento com adição mineral incorporada apresentou mesma taxa de ataque que os demais (sem adição), entretanto a partir do momento que toda a portlandita foi consumida, iniciou-se um processo de descalcificação do C-S-H, observado pela DRX. / The main point of this research is to propose a fast and effective method of evaluation of the cement reactivity to sulfate attack. Resistance to sulfate attack was measured by determining the combined sulfate in cement paste samples with exposure to Na2SO4 and MgSO4 solution, at high temperature (65°C). The samples of cement paste was triturated (powdered) in the proposed method. The results of combined SO3 showed that the Class G cement was little less susceptible to the sulfate attack because it has larger amount of Fe2O3. The ettringite formation was observed in the attack for both sulfate salts; and gypsum formation in the attack for MgSO4 (results of TG and XRD). The blended cement presented same results that the others, however when the Ca(OH)2 was totally consumed, it observed the decalcification of the C-S-H, by XRD.

Fosfogesso é um resíduo sólido da produção de ácido fosfórico pelas indústrias de fertilizantes. A produção anual deste material no mundo é de cerca de 180 milhões de toneladas, e isto causa problemas com a sua armazenagem. O fosfogesso tem sido estudado para uso como material de construção de bases e sub-bases de pavimentos. O fosfogesso tem pouca durabilidade frente à ação da água quando sujeito somente à estabilização mecânica. O cimento Portland é então adicionado ao fosfogesso, resultando em misturas mais estáveis. A reação do aluminato tricálcico contido no cimento e dos sulfatos presentes no fosfogesso poderia conduzir à formação de cristais de etringita e à expansão subseqüente. O objetivo desta pesquisa é avaliar a influência do tipo de cimento na expansibilidade das misturas de fosfogesso e cimento para uso na construção de pavimentos. Analisou-se o comportamento expansivo de corpos de prova compactados com diferentes proporções de fosfogesso e cimento, variando-se o tipo de cimento, energia de compactação e período de cura. Para todos os cimentos usados nesta pesquisa, considerando-se o período de 84 dias de cura, a maior parte da expansão ocorreu nos primeiros 28 dias. A influência do tipo de cimento na expansão das misturas de fosfogesso e cimento é significante, mas o teor de aluminato tricálcico não é a única explicação para o comportamento de expansão observado neste estudo, visto que os resultados experimentais indicam que quantidades crescentes de aluminato tricálcico conduzem a menores expansões, fato que contraria a expectativa inicial desta pesquisa. / Phosphogypsum is a solid by-product resulting from the phosphoric acid process for manufacturing fertilizers. The annual worldwide production of this material is about 180 million de tons and it causes problems with its disposal. The phosphogypsum has been studied for use in pavement base and sub-base materials. Phosphogypsum has poor durability when subjected to mechanical stabilization only in wet conditions. The addition of stabilizing materials, such as Portland cement, is one method of overcoming this deficiency. The chemical reaction between tricalcium aluminate present in Portland cement and sulfate ions supplied by phosphogypsum could lead to the formation of ettringite and subsequent expansion. The objective of this research is to evaluate the influence of Portland cement type on the expansion of cement-stabilized phosphogypsum mixtures for use as pavement construction. The expansion behavior was analyzed through compacted specimens composed by different phosphogypsum and cement proportions, varying the cement type, compaction energy and curing period. For all cements used in this research, most of expansion occurred within the first 28 days in relation to the 84 days of curing. There is a significant influence of cement type on the expansion of the cement-stabilized phosphogypsum mixtures, but the aluminate tricalcium content is not the only explanation for the expansion behavior observed in this study. The experimental results show that an increasing amount of tricalcium aluminate yields lower expansion, fact that thwarts the initial expectation of this research.

La cristallisation du sel dans les pores peut conduire à l'expansion d'une variété de milieux poreux, y compris le béton, la pierre ou les sols. Par exemple, les attaques sulfatiques de matériaux cimentaires peuvent conduire à des cristallisations du gypse ou de l’ettringite, qui peuvent causer un endommagement et limiter la durabilité des structures en béton. Une meilleure compréhension de la façon dont la cristallisation induit la déformation des matériaux cimentaires est une condition préalable à la conception de moyens efficaces pour atténuer les effets néfastes de la cristallisation du sel. Dans cette thèse, nous cherchons à comprendre comment la cristallisation conduit à l'expansion, pour les matériaux à base de ciment dans le cas spécifique de la présence d'ions sulfatiques, qui est un cas pertinent pour la compréhension des attaques sulfatiques. La principale originalité de l'étude a été de réaliser des expériences avec des matériaux granulaires compactés dans des cellules œdométriques ou isochores. Les échantillons testés ont été fabriqués par broyage de pâtes de C3S, de pâtes de ciment Portland ordinaire, ou des mélanges des phases dont ces pâtes sont constituées (par exemple, monosulfoaluminate AFm), puis de les compacter dans des éprouvettes cylindriques sur une hauteur de 2 cm. Dans les cellules, les échantillons compactés sont très perméables et peuvent être saturés avec des solutions de sulfate de sodium en moins d’1 heure. Dans une cellule œdométrique, l'échantillon est empêché de se dilater radialement, mais est autorisé à se dilater axialement: nous avons mesuré comment des injections de solutions induisent une expansion axiale. Dans une cellule isochore, l'échantillon est empêché de se dilater à la fois radialement et axialement: nous avons mesuré comment des injections de solutions provoquent le développement de contraintes axiales et radiales. Un point notable des cellules isochores que nous avons développées est que toute solution s’évacue le long de l'échantillon et peut être récupérée: ainsi, à partir des mesures des concentrations et des volumes de solutions d'entrée et de sortie, la quantité de sulfates restant dans l'échantillon au cours des expériences pourrait être déterminée. En parallèle des mesures de déformation/contrainte, nous avons effectué des caractérisations minéralogiques et microstructurales des échantillons en utilisant une variété de techniques, notamment : la fluorescence X, l’analyse thermogravimétrique, la diffraction des rayons X, la résonance magnétique nucléaire d'aluminium et la microscopie électronique à balayage avec analyse aux rayons X. Les évolutions des concentrations de sortie et de la minéralogie au cours du processus d'injection ont pu être bien prédites avec le logiciel CHESS de modélisation géochimique. Les résultats expérimentaux de la campagne, en conjonction avec les résultats des caractérisations minéralogiques et microstructurales, ont permis de révéler quels sont les principaux paramètres qui régissent l'expansion. Grâce à ce protocole original que nous avons développé, l'expansion ou le développement de contraintes a commencé immédiatement après l'injection de la solution, s’est stabilisé au bout de quelques jours à quelques semaines, et la cristallisation a eu lieu de façon homogène sur toute la hauteur de l'échantillon. En outre, nous avons montré que la cristallisation du gypse contribue à l'expansion. Dans les tests isochores, nous montrons que les deux cristallisations d'ettringite et de gypse peuvent induire des contraintes, et que l'amplitude de ces contraintes dépend linéairement du volume de ces cristaux formés. Les conclusions tirées de cette étude expérimentale permettent de mieux comprendre les processus physiques par lesquels la cristallisation induit une expansion ou des contraintes dans des solides poreux, et permettent d’orienter la modélisation des attaques sulfatiques dans les matériaux cimentaires / In-pore crystallization can lead to expansion of a variety of porous media, including concrete, stone, or soils. For instance, sulfate attacks of cement-based materials can lead to crystallizations of gypsum or ettringite, which may cause damage and limit the durability of concrete structures. A better understanding of how crystallization induces deformation of cementitious materials is a prerequisite to designing efficient ways of mitigating the detrimental effects of salt crystallization. In this thesis, we aim at understanding how crystallization leads to expansion, for cement-based materials in the specific case of the presence of sulfate ions, which is relevant for sulfate attacks. The main originality of the study was to perform experiments with granular materials compacted into oedometric or isochoric cells. The tested samples were manufactured by grinding C3S pastes, regular Portland cement pastes, or mixtures of phases of which those pastes are made (e.g., monosulfoaluminate AFm), and then compacting them within the cell into 2-cm-high cylindrical specimens. In the cells, the highly permeable compacted samples could be flushed with sodium sulfate solutions in less than 1 hour. In an oedometric cell, the sample is prevented from expanding radially, but is allowed to expand axially: we measured how injections of solutions induced an axial expansion. In an isochoric cell, the sample is prevented from expanding both radially and axially: we measured how injections of solutions induced the development of axial and radial stresses. A salient feature of the isochoric cells we developed is that all solution flushed throughout the sample could be recovered: thus, from the measurements of concentrations and volumes of input and output solutions, the amount of sulfate remaining in the sample over the experiments could be determined. In parallel to the deformation/stress measurements, we also performed the mineralogical and microstructural characterizations of the samples before and after testing by using a variety of techniques, including X-ray fluorescence, thermogravimetric analysis, X-ray diffraction, aluminum nuclear magnetic resonance and scanning electron microscopy with X-ray analysis. The evolutions of the output concentrations and of the mineralogy over the injection process could be well predicted with the geochemical modeling software CHESS. Experimental results of the campaign, in conjunction with results from mineralogical and microstructural characterizations, made it possible to reveal what the main parameters are that govern expansion. Thanks to the original protocol we developed, expansion or development of stresses started immediately after the injection of solution, stabilized after a few days to a few dozen days, and crystallization occurred homogeneously throughout the height of the sample. One interesting conclusion is that, even when ettringite crystallizes in macropores, i.e., outside of the C-S-H gel porosity, ettringite can lead to an expansion. Also, we showed that gypsum crystallization contributes to expansion. In isochoric testing, we showed that both crystallization of ettringite and of gypsum can induce stresses, and that the magnitude of those stresses is linearly related to the volume of those crystals formed. The conclusions drawn from this experimental study make it possible to better understand the physical processes through which crystallization induces expansion or stresses in porous solids, and thus to orient the modeling of sulfate attacks in cement-based materials

Up to present, ettrigite has been prepared by two means in the Institute of Technology of Building Materials and Components of the BUT Faculty of Civil Engineering: originally by the hydration of the yeelimite clinker; recently by the direct synthesis of ettringite from calcium hydroxide and aluminum sulfate, the latter being considered more suitable in qualitative and quantitative terms. This diploma thesis focuses on the comparison of both means, using ettringite produced by the latter as control sample. This endeavor focuses on monitoring the stability of ettringite and its possible conversion to other minerals using X-ray diffraction analysis, thermal analysis and scanning electron microscopy (SEM).

No description available.

For repairing concrete transportation infrastructure, such as pavements and bridges, much importance is placed on early-age strength gain as this has a major impact on scheduling and opening to traffic. However, the long-term performance and durability of such repair materials are often not satisfactory, thus resulting in future repairs. This research project focuses on the evaluation of the durability of various rapid-setting cementitious materials. The binders studied in this project include calcium aluminate cement (CAC), calcium sulfoaluminate cement (CSA), Type III portland cement, alkali-activated fly ash (AAFA) , and various prepackaged concrete materials. In addition, selected CAC and CSA mixtures were further modified with the use of a styrene-butadiene latex. The durability aspects studied include freezing-and-thawing damage and the implications of air entrainment in these systems, alkali-silica reaction, sulfate attack, and permeability of the concrete matrix and potential corrosion. / text

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No. of bitstreams: 2 Dissertação Danilo G Batista 2013_ Final.pdf: 14272139 bytes, checksum: 1046108060b4c8d18c18e82aa11daf9d (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2013-10-21 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / A long time ago aggregate particles were considered inert but this concept is no longer adequate. Expansive reactions resulting from the oxidation of sulfide-bearing aggregates and the AAR are examples of potential chemical interactions that aggregates may experience in concrete, depending on the surrounding environment. This research is an investigation into concrete deterioration in Hydroelectric Power Plants (HPPs), focusing on aggregate reactions relating to attack by sulfates, due to oxidation of sulfide minerals, as well as to the alkali-aggregate reaction (AAR). One of the main purposes is to have a clearer understanding of the changes in sulfide minerals occurring in aggregates and verify their influence on concrete durability as well as check the conditions and characteristics that maximize or not the synergy of such pathology. Along with that, another purpose is to study the possibility of the AAR occurring in the same structures. To this end, an investigation of concrete structures extracted from five Brazilian hydroelectric plants, namely Corumbá HPP, Marechal Mascarenhas de Moraes HPP, Paulo Afonso II HPP, Paulo Afonso IV HPP and Moxotó HPP, was conducted. In addition to the concretes, a study of the rocky material and aggregates surrounding the plants that were of the same origin as the aggregates in the concretes was also performed. A thorough visual inspection was made in the field of some concrete structures selected from the HPPs , with the subsequent extraction of concrete cores in spots that were more prone to the incidence of some chemical reaction. The concrete core samples were initially inspected in the laboratory to check for possible visible anomalies on their surfaces, and were subsequently subjected to laboratory tests to determine the mechanical properties such as compressive strength and elasticity modulus. Chemical and microstructural analyses of the concrete were then carried out, in addition to the reconstitution of the mix design and determination of their pH. The concrete were also underwent internal inspections before the microstructural analyses, and the last were scanning electron microscopy with energy-dispersive X-ray spectrometry (EDS) and X-ray diffraction (XRD) in order to diagnose deterioration. Aggregates extracted from concrete cores along with the rocky material of the same origin were also subjected to chemical and mineralogical analyses. The concrete from Corumbá HPP was found to be sound, but in the concretes from the other HPPs it was proved the incidence of AAR and sulfate attack simultaneously, and in some cases, with evidences that the attack by sulfates results from the oxidation of sulfide minerals in the aggregates. / Durante muito tempo as partículas de agregados foram consideradas inertes; entretanto, atualmente esse conceito foi banido. Reações expansivas decorrente da oxidação de minerais sulfetos presentes em agregados e da reação álcali-agregado (RAA) são exemplos de interações químicas potenciais que os agregados podem experimentar quando presentes no concreto, dependendo do meio circundante. A presente pesquisa aborda a investigação de concretos de UHEs com foco na deterioração por reações com os agregados no que tange ao ataque por sulfatos, devido à oxidação de minerais sulfetos, bem como à RAA. Objetiva-se avançar no entendimento do fenômeno de alteração de minerais sulfetos presentes em agregados e verificar a sua influência sobre a durabilidade de concretos, além de verificar as condições e características que maximizam ou não a sinergia desta patologia. Conjuntamente, pretende-se também estudar, nas mesmas estruturas, a possibilidade de ocorrência da RAA. Para tanto, procedeu-se com uma investigação de concretos extraídos de estruturas pertencentes a cinco usinas hidrelétricas brasileiras, a saber: UHE Corumbá, UHE Marechal Mascarenhas de Moraes, UHE Paulo Afonso II, UHE Paulo Afonso IV e UHE Moxotó. Além dos concretos, procedeu-se também com um estudo do material rochoso e dos agregados do entorno das usinas, de mesma origem que os agregados dos concretos. Inicialmente foi realizada criteriosa inspeção visual em campo de algumas estruturas de concreto selecionadas das UHEs, com posterior extração de testemunhos em locais com maior propensão da incidência de alguma reação química. Os testemunhos de concreto foram inicialmente inspecionados em laboratório para a verificação de possíveis anomalias visíveis em suas superfícies, sendo posteriormente submetidos a ensaios laboratoriais para a determinação das propriedades mecânicas de resistência à compressão e módulo de elasticidade. Foram, na sequência, realizadas análises químicas e microestruturais dos concretos, além da reconstituição de traço e obtenção do pH. Os concretos também foram submetidos a inspeções internas antes das análises microestruturais, sendo estas últimas a microscopia eletrônica de varredura com espectrometria por energia dispersiva de raios X (EDS) e a difração de raios X (DRX), ambas com o objetivo de diagnosticar deterioração. Os agregados extraídos dos concretos juntamente com o material rochoso de mesma origem também foram submetidos a análises químicas e mineralógicas. Pelos resultados, verificou-se boa integridade dos concretos da UHE Corumbá, porém para as demais usinas, constatou-se nos concretos a incidência de RAA, além de ataque por sulfatos, tendo alguns dos concretos das demais usinas indícios de que o ataque por sulfatos é decorrente da oxidação de minerais sulfetos presentes nos agregados.

La cantidad de residuos se ha incrementado con el paso del tiempo, siendo actualmente una amenaza grave para el medio ambiente; tal es el caso del vidrio plano, el cual genera cantidades considerables de merma poco reutilizables en su producción. Esto ha generado que sus residuos reciban una mayor atención por las autoridades e investigadores a nivel global en los últimos años, proponiéndose usos respetuosos que contribuyan hacia un entorno más sostenible. Este estudio profundiza en la utilización del residuo de vidrio plano para la reducción de su merma y lo propone como una solución en la elaboración de un concreto ecológico, al ser incluido de forma pulverizada como adición en el concreto. Para ello, se hicieron diferentes diseños de mezcla con porcentajes variables de vidrio plano pulverizado, realizándose comparaciones con respecto a un concreto patrón para identificar su efecto en las propiedades del concreto; evaluándose los ensayos de asentamiento, resistencia a la compresión y resistencia a la compresión en condiciones de ataque por sulfatos. Los resultados muestran que la adición de vidrio plano pulverizado contribuye a la mejora del asentamiento, la resistencia a la compresión y la resistencia a la compresión en condiciones de ataque por sulfatos; y también, presenta un ahorro económico con respecto al concreto patrón. / The amount of waste has increased over time, currently being a serious threat to the environment. Such is the case of flat glass, which generates considerable quantities of waste that are not reusable in the production. This has generated that its residues receive a greater attention by the authorities and researchers to global level in the last years, proposing respectful uses that contribute towards a more sustainable surroundings. This study deepens in the use of the flat glass waste to reduce its shrinkage and proposes it as a solution in the elaboration of an ecological concrete. For this, different mixing designs were made with varying percentages of flat sprayed glass, making comparisons with respect to a concrete pattern to identify its effect on concrete properties; evaluated by slump tests, compressive strength and compressive strength in sulfate attack conditions. The results show that, the addition of pulverized flat glass contributes to the improvement of slump, compressive strength and compressive strength under sulphate attack conditions; and it presents an economic saving with respect to the reference concrete. / Trabajo de investigación