The cement industry contributes around 5-7% of man-made CO2 emissions globally because of the Portland Cement (PC) production. Therefore, innovative reactive magnesia cement, with significant sustainable and technical advantages, has been proposed by blending reactive MgO and hydraulic binders in various proportions. MgO is currently produced from the calcination of magnesite (MgCO3), emitting more CO2 than the production of PC, or from seawater/brine which is also extremely energy intensive. Hence this research aims to investigate an innovative method to produce MgO from reject brine, a waste Mg source, through carbon sequestration, by its reaction with CO2, to provide a comparable low carbon manufacturing process due to the recycling of CO2. The produced deposits are then calcined to oxides with potential usage in construction industry. The entire system is a closed loop to achieve both environmental optimisation and good productivity. This research focuses on the chemical manufacturing process, integrated with material science knowledge and advancements, instead of concentrating purely on chemistry evaluations. Six series of studies were conducted, utilising MgCl2, CaCl2, MgCl2-CaCl2, MgCl2-CaCl2-NaCl, and MgCl2-CaCl2-NaCl-KCl to react with CO2 under alkaline conditions. The precipitates include hydrated magnesium carbonates, calcium carbonates and magnesian calcite. Generated carbonates were then calcined in a furnace to obtain MgO, CaO or dolime (CaO•MgO). All six series of carbonation processes were carried out under a controlled pH level, to study the constant pH’s effect on the process and resulting precipitates. Other controllable factors include pH, temperature, initial concentration, stirring speed, and CO2 flux rate. In conclusion, the optimum parameters for the production of the carbonated precipitates are: 0.25MgCl2 + 0.05CaCl2 + 2.35NaCl + 0.05KCl, 700rpm stirring speed, 25oC room temperature, pH=10.5, and 500cm3/min CO2 infusion rate. Reaction time is within a day. These parameters are chosen based on the sequestration level, particle performance morphology and the operational convenience. The optimum calcination parameters are at 800oC heating temperature with a 4h retention time.

第22回名古屋大学年代測定総合研究センターシンポジウム平成21(2009)年度報告

The carbonation in concrete is caused by the penetration of environmental carbonic anhydride (CO2) in concrete by diffusion, being considered one of more important structures pathologies. It occurs naturally in concrete structures, from the surface and causes the alkalis neutralization reactions, depassivating the rebars and its corrosion possibility. In this study the concrete investigation with 14 years old composed by binary and ternary mixtures of pozzolans as silica fume (10%), fly ash (25%), rice husk ash (25%), fly ash and silica fume (15+10)% and fly ash with rice husk ash (10+15)%. The natural carbonation depths were measured in cylindrical specimens with 0,5, 1, 2, 4 and 14 years readings, exposed in lab internal environment, in normal conditions of temperature and CO2 concentrations. Natural carbonation coefficients in the five cited ages were calculated, in equality of water/binder (w/b) relationship (0.35, 0.45 and 0.55), and 50 and 60 MPa axial compressive strength, and the results were compared with the short term tests (accelerated). Microstructure analysis by means of remained calcium hydroxide, hydrated compounds by DRX, porosity by Hg intrusion porosimetry and visual analysis by MEV and EDS were accomplished. Among the pozzolans mixtures the silica fume (10%) presented lower carbonation for w/b 0.35 and 0.45. For w/b 0.55 the better performance occurred to the fly ash and rice husk ash ternary mixture. The relationships between accelerated and natural carbonation coefficients showed decrease of the natural coefficients related to the accelerated ones, in a relation that varied between 1,0 and 2,0 (mean) for the pozzolanic mixtures. In 50 and 60 MPa compressive strength equality, the carbonation depended of the pozzolan type and content, being influenced by the chemical and physical properties of each one in particular. The microstructure tests results confirmed the CH decrease in the carbonated layer and the CaCO3 increase, and the hydrated silicates and silicoaluminates depolymerization. According NBR 15575-5 was observed that it is possible to obtain concretes with until 25% of pozzolans with performance of the project useful life, in front of carbonation, of 60 years. / A penetração de anidrido carbônico (CO2) ambiental por difusão no concreto ocasiona a carbonatação, sendo considerada uma das patologias mais importantes das estruturas. Acontece naturalmente nas estruturas de concreto, a partir da superfície e ocasiona reações de neutralização dos álcalis, despassivando a armadura e a possibilidade de sua corrosão. Neste estudo apresenta-se a investigação de concretos com 14 anos de idade, compostas de misturas binárias e ternárias de pozolanas sendo sílica ativa(10%), cinza volante(25%), cinza de casca de arroz(25%), cinza volante e sílica ativa (15+10)% e cinza volante com cinza de casca de arroz (10+15)%. As profundidades de carbonatação natural foram medidas em corpos de prova cilíndricos, com leituras a 0,5, 1, 2, 4 e 14 anos, expostos em ambiente interno de laboratório, em condições normais de temperatura e concentração de CO2. Calculou-se os coeficientes de carbonatação natural nas 5 idades citadas, em igualdade de relação a/ag (0,35, 0,45 e 0,55) e de resistência à compressão axial de 50 e 60 MPa, e comparou-se com os resultados de curto prazo (acelerado). Realizou-se análise da microestrutura por meio do teor de hidróxido remanescente, dos compostos hidratados por difração de raios-X, porosidade por porosimetria por intrusão de mercúrio e análise visual por microscopia eletrônica de varredura com EDS. O concreto de referência apresentou menor coeficiente de carbonatação nas três relações a/ag estudadas. Entre as misturas com pozolanas a sílica ativa (10%) apresentou menor carbonatação para a/ag 0,35 e 0,45. Para a/ag 0,55 o melhor desempenho aconteceu para a mistura ternaria de cinza volante e cinza de casca de arroz. As relações entre os ensaios acelerado e naturais mostraram decréscimo dos coeficientes de carbonatação natural em relação aos acelerados, numa relação que variou, em média, entre 1,0 e 2,0 para as mistura pozolânicas. Em igualdade de resistência à compressão de 50 e 60 MPa a carbonatação dependeu do tipo e do teor de pozolana, sendo influenciada pelas propriedades químicas e físicas de cada uma em particular. Os resultados dos ensaios da microestrutura confirmaram o decréscimo do CH nas camadas carbonatadas e acréscimo de CaCO3 e a despolimerização dos silicatos e silicoaluminatos de cálcio hidratados. Segundo a NBR 15575-2 observou-se que é possível obter-se concretos com até 25% de pozolanas, com desempenho à vida útil de projeto, frente a carbonatação, de 60 anos.

The intrusion of chlorides and carbon dioxide into a reinforced concrete (RC) structure can initiate corrosion of the reinforcing steel, which, due to its expansive nature, can damage the structure and adversely affects its serviceability and safety. Corrosion will initiate if at the steel surface the concrete free chloride concentration exceeds a defined limit, or its pH falls below a critical level. Hence, determination of the time to reaching these critical limits is key to the assessment of RC structures durability and service life. Due to the ionic nature of the chlorides and the bicarbonate anion (HCO3-) formed by the CO2 in the multi-ionic pore solution, the transport of both species is driven by Fickian diffusion combined with electromigration and ionic activity, which can be mathematically expressed by the Nernst-Planck-Poisson (NPP) equations. For a complete representation of the phenomenon, however, the NPP equations must be supplemented by the relevant chemical equilibrium equations to ensure chemical balance among the various species within the concrete pore solution. The combination of NPP with the chemical equilibrium equations is often termed the NPP reactive transport model. In this study, such a model is developed, coded into the MATLAB platform, validated by available experimental data, and applied to analyze the time-dependent concrete carbonation and the movement of chlorides in carbonated and non-carbonated concrete. The results of these analyses can be used to predict the time to corrosion initiation. The transient one-dimensional governing equations of NPP are numerically solved using the Galerkin’s finite element formulation in space and the backward (implicit) Euler scheme in the time domain. The associated system of chemical equilibrium equations accounts for the key homogeneous and heterogeneous chemical reactions that take place in the concrete during carbonation and chlorides transport. At each stage of the analysis, the effects of these reactions on the changes in the pore solution chemical composition, pH, cement chloride binding capacity, concrete porosity, and the hydrated cement solids volumetric ratio are determined. The study demonstrates that given accurate input data, the presently developed NPP reactive transport model can accurately simulate the complex transport processes of chlorides and CO2 in concrete as a reactive porous medium, and the ensuing physical and chemical changes that occur due to the reaction of these species with the pore solution and the other cement hydration products. This conclusion is supported by the good agreement between results of the current analyses with the corresponding available experimental data from physical tests involving carbonation, and chloride diffusion in non-carbonated and carbonated concrete. / Thesis / Doctor of Philosophy (PhD)

Three sets of concrete blocks were cast to investigate the effects of natural exposure conditions, at the macro and microclimate scale, and field curing on the performance and durability of OPC and OPCjGGBS concretes. These are termed the Loughborough winter series, the Loughborough summer series and the Muscat summer series. Three concrete mixes were investigated in the two Loughborough series (30 and 50 MPa OPC concrete mixes and a 30 MPa OPCjGGBS concrete mix) and two in the Muscat weather series (the two 30 MPa concretes). A group of specimens were cast with each mix consisting of 600 x 500 x 150mm concrete blocks plus control cubes and prisms. The samples were cured in-situ and exposed to a range of curing methods and microclimates. Surface zone properties (up to 50mm depth) were evaluated by air permeability, sorptivity, carbonation, thermogravimetry (TG) and mercury intrusion porosimetry (MIP) tests, conducted after 3 and 12 months of site exposure. The results revealed distinct variations due to macroclimate, microclimate, curing, concrete type and age. The air permeability, sorptivity and carbonation of the concrete exposed under moderate and rainy conditions of a Loughborough summer season were lower than identical concrete cast and cured during a very cold and dry Loughborough winter season. Further, the sorptivity of concrete subjected to the hot and dry climatic conditions of Muscat was significantly higher than companion samples subjected to the temperate Loughborough climate. Significant variations in properties were observed within the two sides of the same concrete element, each subjected to a different microclimate. The air permeability, sorptivity, carbonation and porosity were reduced with increased hessian curing duration. However, premature drying of wet hessian during curing had an adverse effect on concrete quality as this produced concrete of higher permeability and carbonation than non-cured concrete. The application of controlled permeability formwork was effective in improving the concrete's sub-surface properties. The curing affected zone (CAZ) extended to approximately 20mm below the surface of the concrete that was exposed to the Loughborough winter and summer climate, and 40-50mm for the concrete exposed to the Muscat climate, with notable variation in properties due to climate and curing. The TG and MlP results provided insights into the mechanisms associated with the variations in the three concrete's properties due to natural field exposure.

Whey is a byproduct of cheese making; whey proteins are globular proteins which can be modified and polymerized to add functional benefits, these benefits can be both nutritional and structural in foods. Modified proteins can be used in non-foods, being of particular interest in polymer films and coatings. Food packaging materials, including plastics, can linings, interior coatings of paper containers, and beverage cap sealing materials, are generally made of synthetic petroleum based compounds. These synthetic materials may pose a potential human health risk due to presence of certain chemicals such as Bisphenol A (BPA). They also add to environmental pollution, being difficult to degrade. Protein-based materials do not have the same issues as synthetics and so can be used as alternatives in many packaging types. As proteins are generally hydrophilic they must be modified structurally and their performance enhanced by the addition of waterproofing agents. Polymerization of whey proteins results in a network, adding both strength and flexibility. The most interesting of the food-safe waterproofing agents are the (large aspect ratio) nanoclays. Nanoclays are relatively inexpensive, widely available and have low environmental impact. The clay surface can be modified to make it organophilic and so compatible with organic polymers. The objective of this study is the use of polymerized whey protein (PWP), with reinforcing nanoclays, to produce flexible surface coatings which limit the transfer of contents while maintaining food safety. Four smectite and kaolin type clays, one treated and three natural were assessed for strengthening qualities and the potential waterproofing and plasticizing benefits of other additives were also analyzed. The nutritional benefits of whey proteins can also be used to enhance the protein content of various foodstuffs. Drinkable yogurt is a popular beverage in the US and other countries and is considered a functional food, especially when produced with probiotic bacteria. Carbonation was applied to a drinkable yogurt to enhance its benefits. This process helps reduce the oxygen levels in the foodstuff thus potentially being advantageous to the microaerophilic probiotic bacteria while simultaneously producing a product, somewhat similar to kefir, which has the potential to fill a niche in the functional foods market. Yogurt was combined with a syrup to reduce its viscosity, making it drinkable, and also to allow infusion of CO2. This dilution reduced the protein content of the drink and so whey protein concentrate was added to increase levels in the final product. High-methoxyl pectins were used to provide stability by reducing the tendency of the proteins to sediment out. The objectives of this study were to develop a manufacturing technology for drinkable carbonated symbiotic yogurts, and to evaluate their physicochemical properties. Two flavors of yogurt drink, pomegranate and vanilla, were formulated containing inulin as prebiotic, along with probiotic bacteria, producing symbiotic dairy beverages.

La carbonatation atmosphérique et la pénétration des ions chlorures sont les principales causes du déclenchement de la corrosion des armatures dans les bétons armés. Chacun de ses mécanismes a fait l'objet de nombreuses études dans la bibliographie. Pourtant les études prenant en compte en même temps les deux types d'agression sont rares. Le couplage des deux phénomènes existe cependant. La carbonatation intervient en effet dans tout ouvrage dès le décoffrage et il suffit que cet ouvrage soit aussi par exemple situé à proximité d'eau de mer pour que les embruns apportent des ions chlorures dans le matériau. L'objectif de cette thèse a été de quantifier les différentes phases de la matrice cimentaire et ses capacités de fixation des ions chlorures par le biais d'isothermes d'interactions pour des matériaux sains et carbonatés. Ces isothermes d'interactions obtenues notamment par la méthode des équilibres ont permis de voir que les matrices partiellement ou totalement carbonatées fixaient moins d'ions chlorures que les matrices saines. L'utilisation de moyens complémentaires d'analyses tels que l'analyse thermogravimétrique (ATG), la diffraction des rayons X (DRX) et la résonance magnétique nucléaire (RMN) a permis de mieux comprendre cette perte de fixation. Une diminution des sels de Friedel et des chlorures fixés par les C-S-H a été ainsi mise en évidence dans les matériaux carbonatés. Ces diminutions qui on été quantifiées sont attribuées à une modification sous carbonatation des phases capables de fixer les ions chlorures (phases aluminates, sulfo-aluminates et C-S-H). Des différences au niveau du réseau poreux ont été également mises en évidence par la porosimétrie par intrusion de mercure (diminution de la macroporosité et de la connectivité en général pour les matrices carbonatées par formation de CaCO3). L'objectif a été aussi de corréler toutes ces modifications observées avec les propriétés de transport des ions qui ont été obtenues par des tests de diffusion et migration des ions chlorures (et/ou sulfates) ainsi que des mesures de résistivité électrique. Les résultats expérimentaux ont montré que le coefficient de diffusion apparent est plus grand dans les matériaux carbonatés. Certaines expériences de diffusion faites en présence à la fois d'ions chlorures et sulfates ont aussi montré la concurrence de ces deux ions pour se fixer à la matrice cimentaire. Les matériaux cimentaires testés (bétons et pâtes) ont été formulés sans ou avec additions minérales (métakaolin, cendres volantes, laitier) et les propriétés de ces matériaux ont été observées à différents âges / Carbonation and chloride ingress are the main causes of reinforced concrete degradation. A lot of studies describe these two phenomena separately but only few studies state a possible coupling. However, the coupling of both phenomena exists. The corrosion of reinforcement due to chloride ions occurs more often in marine environments or in the presence of deicing salts while carbonation occurs systematically, in a more or less high degree depending on environmental conditions (humidity, temperature…). The aim of this thesis was to quantify the different phases of the cement matrix and its chloride binding by means of chloride binding isotherms for carbonated and non-carbonated cement based materials. These chloride binding isotherms, obtained by the equilibrium method, showed that the partially or totally carbonated cement matrix are bound fewer chlorides than the non carbonated ones. Complementary techniques such as the thermogravimetry (TGA), the X-rays diffraction (XRD) and the nuclear magnetic resonance (NMR) analyses were used and allowed to understand why this binding decrease occurs. A decrease of Friedel's salt and chlorides bound in the C-S-H was showed in the carbonated materials. These decreases were quantified and are due to a modification of the phases containing chloride (such as aluminates, sulfo-aluminates and C-S-H phases) during carbonation process. The porous network, was observed by mercury intrusion porosimetry (MIP), was also modified (decrease of the macroporosity and the connectivity for carbonated cement matrix due to formation of calcium carbonate). The other aim was to correlate all these modifications with the ions transport properties. Chloride diffusion and migration tests (with or without sulfates) were obtained as well as the measurements of electric resistivity. The experimental results showed that the apparent chloride diffusion coefficient is higher in the carbonated cement materials. Some diffusion tests were performed in presence of both chlorides and sulfates, which showed the competition of these two ions to bind on the cement matrix. Cement materials (concrete and cement paste) were designed without or with supplementary cementing materials (metakaolin, fly ash, slag) and the properties of these materials were followed at different curing time

Les bétons de chanvre associent un granulat végétal issu du chanvre, appelé « chènevotte », et une matrice minérale. Ce sont des matériaux isolants répondant particulièrement bien aux nouvelles problématiques environnementales du secteur du bâtiment. Pourtant, leur développement est freiné par d'occasionnels désordres de mise en œuvre et des propriétés mécaniques relativement faibles qui pourraient résulter d'interactions complexes développées entre la chènevotte et le liant. Dans ce contexte, l'objectif des travaux a été de préciser la nature de ces interactions et d'identifier par quels mécanismes celles-ci peuvent modifier la prise du liant et les propriétés finales du matériau. Pour cela, l'évolution de mélanges de matières premières (chènevottes et liants) de natures différentes a été étudiée par des techniques de biochimie, de spectroscopie, de physico-chimie et de mécanique. Cette approche multi-échelle a ainsi permis de mettre en évidence le puissant pouvoir retardateur des produits extraits de la chènevotte sur la prise des liants hydrauliques. Ce retard peut conduire à une absence totale de prise du liant, lorsque celui-ci est couplé à des phénomènes de dégradation de la chènevotte, de migration de ces produits dans la matrice et d'évaporation d'eau. En outre, il a été démontré que les caractéristiques de la chènevotte (composition chimique), la nature du liant (ciment pur ou additionné de chaux), ainsi que les conditions de cure (présence ou non de CO2) sont des facteurs pouvant moduler les effets délétères sur la prise et les propriétés mécaniques du matériau formé. Ils constituent donc des paramètres potentiels d'optimisation des bétons de chanvre. / The hemp concretes, combine a plant aggregate, called “shiv” with a mineral binder. They are insulating materials particularly suited to face the new environmental problems of the building sector. However, their development is hampered by the occasional implementation problems and their relatively low mechanical properties that could result from complex interactions between the shiv and the binder. In this context, the objective of the presented work was to clarify the nature of these interactions and to identify the mechanisms by which they can impact the setting of the binder and the final properties of the material. To do so, the evolution of mixtures of the initial components (shiv and binders) differing by their nature was studied by biochemical, spectroscopic, physical chemistry and mechanical techniques. This multi-scale approach enabled us to highlight the powerful set retarding action of shiv-extractable products on hydraulic binders. This delay can even lead to a total failure of the binder setting when this one is coupled to simultaneous degradation of the hemp aggregate, migration of the formed products in the matrix and water evaporation. Finally, it has been demonstrated that the characteristics of the shiv (chemical composition), the nature of the binder (pure cement or lime added), and the curing conditions (presence or absence of CO2) represent factors that may modulate the deleterious effects on the setting and the mechanical properties of the formed material. They hence constitute potential parameters for the optimization of hemp concretes.

A durabilidade dos edifícios em concreto armado só pode ser alcançada se for atendido um conjunto de requisitos e critérios nas etapas de projeto, execução e manutenção, nas quais os materiais envolvidos precisam ser adequadamente especificados, produzidos e empregados, de acordo com as respectivas rotinas dessas etapas. Assim, o requisito genérico de proteção das armaduras de aço carbono, para a durabilidade de estruturas, é contemplado por vários critérios, desde a etapa de projeto. Esta dissertação trata dos critérios pertinentes à qualidade do concreto e visou contribuir para a evolução de procedimentos para o controle tecnológico de concretos estruturais de cimento Portland, em atmosferas marítimas e urbanas, em clima tropical, com vistas à proteção de armaduras de aço carbono. O programa experimental estudou três lotes diferentes de concretos estruturais, semelhantes quanto a especificações básicas de abatimento: 10 ± 2 cm, de fck 30 MPa e para ambiente classe III da NBR 6118 (2003). O objetivo foi caracterizar e analisar a influência de propriedades físicas do estado fresco sobre o estado endurecido de concretos, dentro da faixa de consistência citada, com ênfase nas propriedades relacionadas ao teor de ar das misturas e suas respectivas resistências à carbonatação e ao ingresso de íons cloreto. A amostragem, os ensaios no estado fresco e a moldagem dos corpos-de-prova foram realizados durante três concretagens conduzidas em duas obras de edifícios de múltiplos andares, na cidade de João Pessoa/PB. As composições e a produção dos lotes ficaram a cargo da central dosadora e fornecedora do concreto em cada obra. O lote inicial serviu para o treinamento da equipe, em campo e laboratório, com amostragem de seis caminhões. Os outros dois lotes, identificados como 1 e 2, foram caracterizados em condições bastante semelhantes, sempre pela mesma equipe, e representados pela amostragem de cinco e seis caminhões, respectivamente. As propriedades medidas no estado fresco foram: abatimento do tronco de cone pela ABNT NBR NM 67 (1998); teor de ar por método pressométrico da ABNT NBR 47 (2002); massa específica pela ABNT NBR 9833 (2008); relação água/materiais secos por analogia à ABNT NBR 9605 (1992); e compactabilidade dos concretos adensado e não adensado, por adaptação da BS EN 12350-4 (2008). Para o estudo das propriedades no estado endurecido, os corpos-de-prova eram cilíndricos, com 10 cm de diâmetro e 20 cm de altura, e foram maturados por dois métodos adaptados do Tipo A da ASTM C 684 (1999). Certas propriedades foram ainda caracterizadas para condições normais de cura da ABNT NBR 5738 (2003). As propriedades estudadas no estado endurecido foram: resistência à compressão pela ABNT NBR 5739 (2007); resistência à tração por compressão diametral pela ABNT NBR 7222 (1994); absorção de água por capilaridade pela ABNT NBR 9779 (1995); absorção de água total e índice de vazios pela ABNT NBR 9778 (2005); resistência à carbonatação em câmara com CO2 (5%; UR 65 + 10 %; 23 + 3 °C); e resistência à penetração de cloretos e CO2, por três ciclos de um dia de molhagem e 27 dias de secagem, entre sete e 91 dias. De modo complementar, foram moldados corpos-de-prova específicos de aço e concreto, para medidas de potencial de circuito aberto, com vistas à continuidade de pesquisas sobre envelhecimento acelerado. A maioria das propriedades foram medidas por duas repetições, constando os resultados individuais em apêndices. A análise inicial dos resultados dos três lotes foi descritiva e resumiu em tabelas o valor médio, desvio padrão, valor máximo, valor mínimo, a amplitude e o coeficiente de variação de cada lote. As propriedades de cada lote também foram comparadas por análise de variância e, ao final, foram correlacionadas de modo conjunto, independentemente do lote de origem. Nesse caso, foram destacadas as melhores correlações entre propriedades, independentemente dos materiais constituintes de cada concreto. Entre as propriedades do estado fresco, destacaram-se as seguintes: a) o abatimento do tronco de cone apresentou correlação forte e inversa (r² = -0,802, para lotes 1 e 2) com resistência à compressão após um dia de cura acelerada em temperatura moderada, em método similar ao Tipo A da ASTM C 684 (1999); b) o teor de ar pelo método pressométrico apresentou correlações de razoáveis a fortes com a resistência à compressão a 28 dias (r² = -0,698, para lotes 1 e 2), com a resistência à tração por compressão diametral por cura acelerada a sete dias (r² = -0,818, para lotes 1 e 2), com a profundidade de carbonatação em câmara de CO2 (r² = 0,699, para lotes 1 e 2) e com a profundidade de penetração de cloretos por três ciclos de imersão e secagem (r² = 0,625, para lotes 1 e 2); c) as medidas de compactabilidade do concreto adensado, ainda que realizadas em condições de campo, apresentaram várias correlações moderadas com outras propriedades do estado fresco e endurecido. No estado endurecido, destacaram-se as seguintes correlações: a) r² da ordem de -0,75 para a resistência à compressão a um dia dos concretos dos lotes 1 e 2, com cura acelerada de 0/24 horas em temperatura moderada, e a profundidade de carbonatação em câmara de CO2 (5%) e a de penetração de cloretos por três ciclos de imersão e secagem, ambas analisadas a 91 dias, tendo os corpos-de-prova recebido cura inicial acelerada de 24/48 h, em temperatura moderada, seguida de imersão normal por até sete dias; b) r² de -0,682 entre a resistência à tração por compressão diametral, com cura acelerada de 24/48h em temperatura moderada seguida de cura normal por até sete dias, e a profundidade de ingresso de íons cloreto, para os três lotes submetidos aos ciclos citados; c) valores de r² entre 0,521 e - 0,561 para as correlações entre a absorção de água por capilaridade, em corpos-de-prova submetidos à cura inicial acelerada em temperatura moderada por 24/48 h e em temperatura normal por até sete dias, e a resistência à carbonatação para os lotes submetidos aos ciclos citados. Assim, esta pesquisa conclui e propõe que, além do teor de ar no estado fresco, as resistências à compressão e à tração por compressão diametral entre um e sete dias, por cura acelerada do Tipo A da ASTM C 684 (1999) ou por duração adaptada da mesma, sejam propriedades que passem a ser avaliadas em concretos, com vistas a melhorar e controlar a sua resistência a agentes agressivos. Nesta pesquisa, a microestrutura nas primeiras idades do concreto mostrou ser mais determinante da rede de conexão de poros e do transporte de agentes agressivos do que a microestrutura em idades mais avançadas de hidratação; e trabalhos futuros devem confirmar esta interpretação. Espera-se que estes resultados possam estimular novas práticas de qualificação de concretos em estudos de dosagem ou no ato do recebimento de concretos pré-misturados, especialmente em ambientes mais agressivos às armaduras, com vistas à futura evolução de procedimentos da ABNT NBR 12655 (2006). / Durability of reinforced concrete buildings can only be achieved if a set of requirements and criteria is met in the design, execution and maintenance phases, in which the materials must be properly specified, manufactured and employed, according to the respective procedures of these phases. Therefore, the general requirement of protection of carbon steel reinforcements, for structural durability, is contemplated by several criteria as early as the design phase. This thesis addresses the relevant criteria concerning concrete quality and its objective was to contribute to the evolution of technological control procedures for Portland cement structural concretes, in urban and maritime atmospheres in tropical climate, aiming at the protection of carbon steel reinforcements. The experimental program studied three different batches of structural concrete that were similar in terms of slump test basic specifications: 10 ± 2 cm, fck = 30 MPa and class III of ABNT NBR 6118 (2003) environmental classification. The goal was to characterize and analyze the influence of physical properties of fresh concrete on hardened concrete, within the previously mentioned consistency range, with emphasis on those properties related to air content of the mixtures and their respective carbonation and chloride ion penetration resistances. Sampling, fresh concrete tests and specimen molding were conducted during three cast-in-place concretes in two construction sites of multi-storey buildings in the city of João Pessoa, state of Paraíba, in Brazil. The batch plant supplying the concrete for each construction site was responsible for batch composition and production. The initial batch was used to train the team, in the field and laboratory, with a sample of six trucks. The other two batches, identified as 1 and 2, were characterized under very similar conditions, always by the same team, and the samples consisted of five and six trucks, respectively. The properties measured in fresh concrete were: slump test according to Brazilian norm ABNT NBR NM 67 (1998); air content by the pressure method of ABNT NBR 47 (2002); bulk density according to ABNT NBR 9833 (2008); water/dry material ratio by analogy with ABNT NBR 9605 (1992); and compactability of compacted and non-compacted concretes, by adaptation of BS EN 12350-4 (2008). In order to study the properties of hardened concrete, the specimens were cylindrical, measuring 10 cm in diameter and 20 cm in height, and were matured by using two methods adapted from Type A of ASTM C 684 (1999). Some properties were also characterized for normal curing conditions according to ABNT NBR 5738 (2003). The properties studied in hardened concrete were: compressive strength according to ABNT NBR 5739 (2007); splitting tensile strength as per ABNT NBR 7222 (1994); capillary water absorption according to ABNT NBR 9779 (1995); water absorption by immersion and void ratio following ABNT NBR 9778 (2005); carbonation resistance in CO2 chamber (5%; 65 + 10 % RH; 23 + 3 °C); and chloride and CO2 penetration resistance, using three one-day wet and 27-day dry cycles, between seven and 91 days. As a complement, specific steel and concrete specimens were molded to measure open circuit potential, aiming at the continuity of researches on accelerated ageing. Most properties were measured twice and the individual results are presented in appendices. Preliminary analysis of results from the three batches was descriptive and summarized in tables the mean value, standard deviation, maximum value, minimum value, amplitude and coefficient of variation for each batch. The properties of each batch were also compared using analysis of variance and, at the end, were correlated as a whole, regardless of the batch of origin. In this case, the best correlations among properties were highlighted, regardless of the materials used in each concrete. Among the properties of fresh concrete, the following are noteworthy: a) the slump test presented strong and inverse correlation (r² = -0.802, for batches 1 and 2) with compressive strength after one day of accelerated curing at moderate temperature, using a method similar to Type A of ASTM C 684 (1999); b) air content in the pressure method presented reasonable to strong correlations with compressive strength at 28 days (r² = -0.698, for batches 1 and 2), with splitting tensile strength with accelerated curing at seven days (r² = - 0.818, for batches 1 and 2), with carbonation depth in CO2 chamber (r² = 0.699, for batches 1 and 2) and with chloride penetration depth after three immersion-drying cycles (r² = 0.625, for batches 1 and 2); c) compactability measurements of compacted concrete, despite being taken in field conditions, presented several moderate correlations with other properties of fresh and hardened concrete. In hardened concrete, the following correlations should be highlighted: a) r² was -0.75 for compressive strength at one day of the concretes from batches 1 and 2, with 0/24- hour accelerated curing at moderate temperature, and carbonation depth in CO2 chamber (5%) and chloride penetration depth after three immersion-drying cycles, both analyzed at 91 days, after the specimens underwent 24/48-hour initial accelerated curing at moderate temperature, followed by normal immersion for up to seven days; b) r² was -0.682 between splitting tensile strength, with 24/48-hour accelerated curing at moderate temperature followed by normal curing for up to seven days, and chloride ion penetration depth, for the three batches submitted to the aforementioned cycles; c) r² values between 0.521 and - 0.561 for the correlations between capillary water absorption, in specimens submitted to initial accelerated curing at moderate temperature for 24/48h and at normal temperature for up to seven days, and carbonation resistance for the batches submitted to the aforementioned cycles. Therefore, this research concludes and proposes that, besides air content in fresh concrete, compressive strength and splitting tensile strength between one and seven days, using accelerated curing of Type A of ASTM C 684 (1999) or for a duration adapted from that norm, are properties that should be evaluated in concrete, with the purpose of improving and controlling resistance to aggressive agents. In this research, the microstructure of the early ages of concrete proved to be more determinant of the pore structure connection and of the transport of aggressive agents than the microstructure at later ages of hydration; and future studies should confirm this interpretation. It is expected that these results will encourage new practices for the qualification of concrete in mixture proportion studies or when ready mixed concrete is received at construction sites, especially in environments that are more aggressive to reinforcements, with a view to developing future procedures of ABNT NBR 12655 (2006).

A carbonatação acelerada é um processo químico que têm se tornado muito atrativa para a indústria do fibrocimento, por mitigar a degradação das fibras vegetais utilizadas nos materiais e por melhorar o desempenho físico-mecânico dos compósitos. Nesse contexto, o presente trabalho avaliou a influência da umidade no processo de carbonatação acelerada, em fibrocimentos reforçados com polpas celulósicas de eucalipto. Para o desenvolvimento das atividades experimentais foi realizado primeiramente um estudo da evolução da carbonatação nos compósitos de fibrocimento, considerando diferentes concentrações de umidade relativa (60, 70, 80 e 90%). Posteriormente, foi realizada a caracterização dos compósitos de fibrocimento por meio da avaliação do desempenho físico-mecânico, com ensaio mecânico de flexão em quatro pontos que determinou o módulo de ruptura (MOR), módulo elástico (MOE), limite de proporcionalidade (LOP) e energia específica (EE); e ensaios físicos para obtenção dos valores de absorção de água (AA), densidade aparente (DA) e porosidade aparente (PA). Os compósitos foram também avaliados quanto à durabilidade e microestrutura, através de ensaios de envelhecimento acelerado, composição mineralógica e análise microestrutural. A partir dos resultados obtidos, os compósitos carbonatados com 60% de umidade relativa apresentaram maior formação de carbonato de cálcio, maior densificação da matriz cimentícia e, consequentemente, menor quantidade de espaços vazios logo nas primeiras horas de carbonatação. Em relação ao desempenho dos compósitos de fibrocimento, as umidades de 60 e 70% permitiram que a carbonatação proporcionasse maiores valores de MOR, LOP e MOE, diferindo estatisticamente dos demais compósitos. Os ensaios físicos complementaram os ensaios mecânicos, mostrando que os compósitos carbonatados com 60 e 70% de umidade apresentaram menores valores de AA e PA, junto de maiores valores de DA. O processo de carbonatação acelerada foi favorecido pelas menores concentrações de umidade relativa, como apresentado também pelas análises de TG e DRX, que permitiram que o processo acontecesse de forma mais efetiva, melhorando a interface fibra-matriz. / The accelerated carbonation is a process that can be made very feasible for the fiber cement industry, for mitigating the degradation of the vegetable fibers used in the materials and for improving the physico-mechanical performance of composites. In this context, the present work evaluated the influence of relative humidity in the accelerated carbonation process in fiber cement composites reinforced with eucalyptus cellulosic pulps. For the development of experimental activities, a study of the evolution of carbonation in fiber cement composites was carried out, considering different concentrations of relative humidity (60, 70, 80 e 90%). Subsequently, the characterization of fiber cement composites was evaluated through the physical-mechanical performance evaluation, with a four-point mechanical test that determined the modulus of rupture, modulus of elasticity, limit of proportionality and specific energy; and physical tests to obtain the values of water absorption, bulk density and apparent void volume. The composites were also evaluated for durability and microstructure, through accelerated aging, mineralogical composition and microstructural analysis. From the results obtained, the carbonate composites with 60% relative humidity showed a higher calcium carbonate formation, a higher densification of the cementitious matrix and, consequently, a lower amount of voids in the first few hours of carbonation. In relation of the performance of fiber cement composites, the 60 and 70% humidity allowed the carbonation to provide higher values of mechanical analysis, differing statistically from the other composites. The physical tests complemented the mechanical tests, showing that the carbonated composites with 60 and 70% humidity presented lower values of water absorption and apparent void volume, with a greater filling of the empty spaces of the composites. The accelerated carbonation process was favored by the lower concentrations of relative humidity, as also shown by the TG and XRD analyzes, which allowed the process to happen more effectively, improving the fiber-matrix interface.