O presente trabalho foi desenvolvido como intuito de estabelecer uma metodologia de dosagem de concreto com uso de cinza volante, objetivo e racionalizado, visando à redução do consumo de cimento e a intensiva utilização de um resíduo poluente, contribuindo para o incremento na sustentabilidade da construção civil pela redução no consumo de clínquer e da liberação de dióxido de carbono para a atmosfera. Foi estabelecida como premissa basilar a hipótese de ser possível relacionar diretamente a trabalhabilidade de um concreto com seu volume de pasta, sendo este tanto menor quanto menor for o volume de vazios da estrutura granular representada pela composição de agregados. Foram empregados quatro agregados, duas areias naturais e duas britas. A mistura das areias foi definida pela menor massa unitária e os agregados graúdos, de maneira a ser obtido o menor volume de vazios. Com a composição de agregados otimizada é definido o volume ótimo de pasta no traço de melhor trabalhabilidade por verificar um dado índice de consistência com o menor teor de água sobre o total de materiais secos. Considerando a cinza volante parte integrante da pasta foram avaliados diferentes critérios para a definição das proporções a serem incorporadas à pasta, tendo como balizamento o volume ótimo de pasta. Foi desenvolvida uma metodologia de cálculo de traços não convencional uma vez que o parâmetro de entrada é a percentagem de substituição de cimento por cinza e não mais a relação água/cimento. Para fins de validação do método proposto foi desenvolvido um estudo baseado no estabelecimento de um paradigma representado por uma dosagem experimental de concreto, sem emprego de cinza volante, que permitiu o cálculo de traços de referência. Com os mesmos materiais e idêntico proporcionamento entre agregados foram desenvolvidas dosagens pelo método proposto que permitiram o cálculo de traços com base nas mesmas resistências à compressão e a comparação através do consumo de cimento calculado em cada situação. É o resultado da presente pesquisa, então, um método de dosagem, no qual a cinza volante é um insumo indispensável, baseado em conceitos diferentes daqueles adotados até então estabelecidos pelos critérios tradicionais da tecnologia do concreto. / This study was developed in order to create and a streamlined methodology of concrete mix proportioning using fly ash to reduce the cement content and an intensive use of a pollutant contributing to the increase of sustainability in construction through reducing consumption of clínquer and the release of carbono dioxide to the atmosphere. It was established as a basic premisse the possibility of connecting directly the workability of concrete with the volume of cement paste used determinate by the most dense aggregate-packing by the smaller volume of voids in the granular structure obtained in composition of many aggregates as necessary. It was used four commercial aggregates, two natural sands and two kind of crushed stone which were commonly found in a construction materials market around Porto Alegre. The sand were mixed according to the mixture that resulted in lower bulk density and coarse aggregate to be obtained the lower volume of voids as possible, being rightly measured. With the composition of aggregate optimized the optimum volume of cement paste that give the best workability with the lower water requirement will be definite. Considering fly ash as a part of the binder it was developed different criteria for define the amount of fly ash to be incorporate in binder having as foundation the volume admitted as responsible for the best workability mixture. To calculation the concrete mix proportions, was adopted an innovative methodology from the percentage replacement of cement by fly ash and no more by the water/cement ratio. The development of the proposed study was based on creating a paradigma represented by a mix-proportioning without fly ash which allowed the calculation of mix proportions of reference. With the same materials and same proportions between the aggregate, were calculated mix proportions to attend the same compressive strength to compare by the cement content of each situation. Thereby the rresults from this study a mix-proportioning method of concrete using fly ash as an imperative input, based in diferentes concepts of given for traditional concrete technology.

AN ABSTRACT OF THE DISSERTATION OF RAJNISH PURI, for the Doctorate of Philosophy Degree in ENGINEERING SCIENCE WITH CONCENTRATION IN CIVIL AND ENVIRONMENTAL ENGINEERING, presented on APRIL 15, 2015 at Southern Illinois University Carbondale TITLE: DEVELOPMENT OF HIGH PERFORMANCE CONCRETE COMPOSITES USING CLASS F FLY ASH AND PCC BOTTOM ASH, AND A STATISTICAL MODEL TO PREDICT COMPRESSIVE STRENGTH OF SIMILAR CONCRETE COMPOSITES ADVISOR: Dr. Sanjeev Kumar It is a common knowledge that the use of concrete is as old as the evolution of human civilization. People have always dreamed beyond the dotted lines and so does the usage of concrete. With the rapid industrialization and globalization, the journey from ordinary concrete to high performance concrete (HPC) has been swift and remarkable. The diversification and utilization of high performance concrete has given the tool in the hands of engineers and architects who can now design and execute buildings of any shape and size deemed impractical a few decades ago. The aim of this research was to develop high performance concrete composites having different percentages of Illinois Class “F” fly ash and bottom ash by replacing the appropriate proportions of Type 1 portland cement and fine aggregate, respectively. The target was to develop high performance concrete composites that have compressive strength of 8,000 psi (55 Mpa) after 28 days of curing in water with a slump of 4±½” (102mm ± 13mm) and air content between 4 and 6 percent. In order to achieve the targeted air content, an air entraining agent DARAVAIR 1400 was used. The water-cement ratio of 0.3 was maintained throughout the research and to achieve the targeted slump, high-range water reducer ADVA 140M was used. The engineering parameters of the high performance concrete composites and an equivalent control mix were evaluated by conducting a detailed laboratory study which included several tests, e.g., slump, fresh air content, compressive strength, splitting-tensile strength, flexural strength, resistance to rapid freezing and thawing, sealed shrinkage and free swelling, and rapid chloride permeability. The results presented show that all high performance concrete composites developed in this study achieved the targeted compressive strength of 8,000 psi (55 MPa) after 28 days of curing in water. The results of the durability tests show that the concrete composites developed in this study have trends similar to that of an equivalent conventional concrete. Based, on the results of this study, it was concluded that the concrete composites have potential to be used on real world projects and thus help the environment by substantially reducing the amount of fly ash and bottom ash going to ash ponds or landfills. Based on the experimental test result data, a detailed statistical analysis was conducted to develop an empirical model to predict compressive strength of similar concrete composites for a given amount of fly ash, bottom ash, and curing period. Additional laboratory tests were performed to validate the mathematical model.

O presente trabalho tem como objetivo o estudo e aproveitamento de cinzas leves da queima de carvão mineral em termoelétrica, como reforço para o Compósito de Matriz Metálica de cobre. Foram estudados diferentes percentuais de cinzas leves como reforço para o cobre, sendo misturados estes pós através de m , compactando os pós em diferentes pressões e sinterizando os corpos de prova obtidos pela compactação. A amostra sinterizada que apresentou a maior dureza entre todos os corpos de prova sinterizados, atingindo 89 HV, foi utilizada como base para a formulação e obtenção de novos corpos de prova, que foram estudados sob condições de moagem dos pós por moinho de bolas e moagem de alta energia. A fabricação do compósito seguiu os padrões industriais do processo de Metalurgia do Pó, como a mistura e moagem dos pós, compactação dos pós e sinterização em atmosfera controlada. Foi realizado o estudo das propriedades físicas e elétricas do compósito formado por cobre e cinzas leves, que comprovou o aumento da dureza para 122 HV, mantendo a condutividade do cobre puro. Este trabalho proporciona uma nova aplicação para as cinzas leves, utilizando estes resíduos de usinas termoelétricas como matéria prima para reforço mecânico na composição de peças à base de cobre, na indústria metalmecânica. / This paper aims to study and use fly ash from coal-fired thermal power plant, as reinforcement for copper Metal Matrix Composite. Different fly ash percentage were studied as reinforcement for copper. The powders were mixed by "Twin V Mixer'', were compacted at different pressures and the compacted samples were sintered. The sintered sample with the highest hardness among all samples reached 89 HV and was used as basis for the formulation and obtaining of new samples, which were studied under controlled conditions of ball milling and mechanical alloying. The manufacture of the composite was made using Powder Metallurgy processes like mixing and milling of powders, compacting of the powders and sintering at controlled atmosphere. A study on the physical and electrical properties of the composite formed by copper and fly ash was carried out proving the hardness increase to 122 HV and maintaining the conductivity of pure copper. This work provides a new application for fly ash using these power plants waste as raw material for mechanical reinforcement in the composition of copper parts in the metalworking industry.

Cinzas de carvão mineral são resíduos gerados em grandes quantidades nas usinas termelétricas. Este é um dos resíduos de maior geração no Brasil, aproximadamente 1,7 milhões de toneladas por ano. A disposição muitas vezes irregular deste resíduo pode causar problemas de ordem ambiental, como contaminação de águas subterrâneas, do solo e desequilíbrio de sistemas ecológicos. Uma possibilidade de uso para estas cinzas é a síntese de zeólitas, que são minerais aluminossilicatos microporosos com propriedades interessantes para uso na indústria. Neste trabalho, estudou-se a síntese de zeólitas a partir de cinzas volantes visando à sua aplicação em dessulfuração de gases. A síntese foi realizada pelo método hidrotérmico, utilizando solução alcalina de KOH e relação solução/sólido de 2 mL g-1. As variáveis estudadas foram temperatura (100 e 150 °C), concentração da solução alcalina (3 e 5 mol L-1) e tempo de reação (8, 24, 48 e 72 h). Os produtos obtidos e as cinzas precursoras foram caracterizados quanto à composição química (FRX), mineralógica (DRX), morfológica (MEV), área específica (BET) e capacidade de troca catiônica (CTC). A partir da determinação das estruturas cristalinas (DRX) foi possível identificar a formação das zeólitas merlinoíta e perlialita em algumas das condições investigadas. O maior valor de área específica BET foi de 102,42 m2 g-1, nas condições de síntese de 150 °C, 5 mol L-1 e 72 h, representando um aumento de 30 vezes em relação à área das cinzas. Os valores de capacidade de troca catiônica ficaram entre 0,71 e 2,02 meq NH4+ g-1 para as diferentes condições estudadas. Com as amostras que apresentaram os melhores resultados nas caracterizações foram realizados testes de dessulfuração e seu desempenho foi comparado com as cinzas precursoras, carvão ativado e zeólita comercial. Foram construídas curvas de ruptura e isotermas de adsorção para esses sistemas. As zeólitas sintetizadas a partir das cinzas apresentaram maiores valores de adsorção máxima. A zeólita que apresentou melhor resultado de adsorção foi a sintetizada nas condições de 150 °C, 5 mol L-1 e 72 h de tempo de reação, sendo esta também a que apresentou maior valor de área específica. Sendo assim, a síntese de zeólitas a partir de cinzas de carvão, geradas no próprio processo de combustão em usinas térmicas, mostra-se como uma potencial aplicação no sentido de que estas podem ser utilizadas na própria usina para adsorção do SO2 gerado durante a combustão. / Coal ash is a waste generated in large quantities in the power plants. This is one of the wastes generated in larger quantities in Brazil, approximately 1.7 million tons per year. The often irregular disposal of this waste can cause environmental problems, such as contamination of groundwater, soil and imbalance of ecological systems. One possibility for using ashes is the synthesis of zeolites, which are microporous aluminosilicate minerals with interesting properties for use in industry. In this work, the synthesis of zeolites from fly ash was studied, aiming its application for gas desulfurization. The synthesis was performed by the hydrothermal method using an alkaline solution of KOH and a solution/solid ratio of 2 mL g-1. The variables temperature (100 and 150 °C), alkaline solution concentration (3 and 5 mol L-1) and reaction time (8, 24, 48 and 72 hours) were studied. The products obtained and the precursory ashes were characterized by its chemical composition (FRX), mineralogical (XRD), morphological (SEM), specific surface area (BET) and cation exchange capacity (CEC). From the determination of the crystalline structures (XRD) it was possible to identify the formation of the merlinoite and perlialite zeolites for some of the investigated conditions. The highest BET surface area was 102.42 m2 g-1 under the synthesis conditions of 150 °C, 5 mol L-1 and 72 hours. This value represented an increase of 30 times in the surface area comparing to the ash. The cation exchange capacity values varied between 0.71 and 2.02 meq NH4+ g-1 for the different conditions studied. Desulfurization tests were carried out for the samples that showed the best characterization results and its performance was compared with the precursor ash, activated carbon and commercial zeolite. Rupture curves and adsorption isotherms were constructed for these systems. The zeolites synthesized from ash showed higher values of maximum adsorption. The zeolite that showed the best adsorption result was synthesized at the conditions of 150 °C, 5 mol L-1 and 72 hours of reaction time, which also had the highest surface area value. Thus, the synthesis of zeolites from coal ash, generated in the combustion process in thermal plants, is shown as a potential application in the sense that these can be used in the plant to adsorb SO2 generated during combustion.

A utilização do concreto auto-adensável (CAA) vem aumentando consideravelmente, no Brasil e no mundo. Com isso, há mais interesse em estudos práticos e teóricos a respeito do material, porém a maioria realizada está centrada em propriedades mecânicas da mistura no estado endurecido. Poucos estudos estão voltados para uma das áreas de maior lacuna: a dosagem. Os métodos de dosagem existentes para o CAA ou são experimentais, baseados na experiência do executor, ou são dependentes de tabelas determinadas a partir de materiais de difícil reprodução em outros locais. Com o intuito de ajudar a resolver este problema, foi proposto um método de dosagem experimental para CAA nesta tese. Este método visa a dosagem de CAA através de ensaios simples que determinem a composição dos agregados, de forma que o empacotamento granular apresente a menor quantidade de vazios possível, a fim de se minimizar o consumo de pasta na mistura. O método utiliza conceitos novos e já consagrados de outros métodos, como o IPT/EPUSP (Helene e Terzian, 1992), o proposto por Tutikian (2004), o de O´Reilly (1992) e o Modelo de Empacotamento Compressivo (CPM) (De Larrard, 1999). Para a comprovação da eficácia deste método, foram dosadas seis famílias de CAA, sendo três com areia fina e outras três com cinza volante, formando pares dosados por diferentes métodos. Entre as seis famílias, duas utilizaram o método de Tutikian (2004) e quatro o método proposto, porém primeiramente com uma faixa de agregado graúdo e após com duas granulometrias de brita, proporcionando famílias com o esqueleto granular mais compacto. Por fim, foi realizada uma família de concreto convencional (CCV). Os CAA dosados através deste novo método são de obtenção mais simples e menos trabalhosa, dependendo menos da experiência do executor, e os resultados mostraram que estes podem ser mais econômicos e com as propriedades no estado endurecido similares ou até vantajosas em relação às dos CCV e a dos outros CAA, principalmente o com duas granulometrias de agregado graúdo. / The utilization of self compacting concrete (SCC) has been increasing considerably throughout Brazil and the world. Hence, there has been more interest in theoretical and practical studies regarding the issue; however, the majority of such studies have been focused on the mechanical properties of the mixture in the hardened state. Very few studies have been focused on the subject of the dosage. The existing methods of dosage for SCC are either experimental, based on the experience of the executor, or are dependent on customized charts based on local materials which are very difficult to reproduce. With the intention to aid in the solution of this problem, an experimental dosage method was proposed in this thesis. This method aims at the dosage of SCC through simple tests that determine the composition of the aggregates, so that the packing density presents the least amount of voids, in order to minimize the consumption of binder in the mixture. The method uses new concepts and some concepts already determined from other methods, such as the IPT/EPUSP (Helene e Terzian, 1992), the one proposed by Tutikian (2004), the O´Reilly (1992) and the Compressive Packing Model (CPM) (De Larrard, 1999). In order to substantiate the efficienty of this method, six families of SCC were carried out, three of those with fine sand and the remaining three with fly ash, forming three pairs dosed by different methods. Amongst the six families, two used the Tutikian method (2004) and the other four families used the proposed method, which were divided into two subgroups; two with one class of gravel and the remaining subgroup utilizing two classes of gravel, supplying each family with a more compact granular skeleton. As a control group, a test family of conventional concrete (CCV) was produced. The SCC designed through this new method is simpler to obtain and requires less labor, depending less on the experience of the executor. The results present themselves as more economical and with the properties in the hardened state quite similar or even enhanced in relation to the ones of the CCV and the other SCC, specially with two classes of gravel.

Este trabalho apresenta um estudo de corrosão da armadura induzida por carbonatação em concretos com elevados teores de cinza volante, utilizando-se para isso a técnica de resistência de polarização. Selecionou-se para a pesquisa quatro relações água/aglomerante (0,44, 0,48, 0,55 e 0,65) e quatro teores de substituição de cimento (clínquer + gesso) por cinza volante (0,15, 30 e 45%). Foi também escolhido para comparação o cimento CPIV 32. Os corpos-de-prova foram curados por 28 dias, sazonados por 22 dias e então carbonatados em ambientes com 5 e com mais de 50% de CO2, por um período 223 dias. Após, os concretos foram parcialmente imersos durante 35 dias. Os ensaios de resistência de polarização foram feitos durante todo o período de carbonatação e imersão parcial. Paralelamente, romperam-se corpos-de-prova por compressão axial, determinou-se profundidades carbonatadas e monitorou-se as massas dos corpos de prova usados para ensaio de resistência de polarização. Realizou-se também análises complementares de microestrutura, utilizando-se as técnicas de difração por raios-X, fluorescência de raios-X, microscopia eletrônica de varredura por elétrons retroespalhados, análises com EDS (Energy Dispersive Spectroscopy) e espectroscopia Raman. Os experimentos realizados possibilitaram identificar o efeito significativo da variação do teor de cinza volante para a corrosão da armadura. Os resultados assim obtidos também permitiram constatar o efeito significativo do teor de CO2 para os resultados de potencial de corrosão e de densidade de corrente de corrosão. Os resultados obtidos neste trabalho evidenciaram a importância de cada vez mais se buscar a realização de ensaios que reproduzam o máximo possível condições de exposição das estruturas no ambiente. / This work presents a study of corrosion of reinforcing steel induced by carbonation in concretes containing fly ash. Four water-binder ratios (0,44; 0,48; 0,55 and 0,65) and four clinker (clinker + gypsum) replacements of fly ash (0;15; 30 and 45%) were selected. It was also chosen CPIV 32 cement to study. After 28 days kept in the moist curing room, the samples were carbonated during 223 days in a CO2 atmosphere with 5% and more than 50% of CO2 After the carbonation period, the concretes samples were partially immersed during 35 days in potable water. Linear polarization resistance tests were made during the whole carbonation and partial immersion periods. Moreover, compressive strength tests were made, depth of carbonation in concretes were determined and the masses of samples used in linear polarization resistance tests were monitored. Even microstructure complementary analyses were made using X-ray diffraction (DRX) techniques, X-ray fluorescence (FRX), electronic microscopy using backscattered electrons and energy dispersive spectroscopy analyses and Raman spectroscopy. Based on the accomplished tests it’s possible to identify the significant effect of the fly ash level replacement in concrete on the reinforcing steel corrosion. The thus gotten results also had of allowed evidencing the significant effect of the CO2 concentration on the results of corrosion potential and corrosion current density.

abstract: The need for sustainability in construction has encouraged scientists to develop novel environmentally friendly materials. The use of supplementary cementitious materials was one such initiative which aided in enhancing the fresh and hardened concrete properties. This thesis aims to explore the understanding of the early age rheological properties of such cementitious systems. The first phase of the work investigates the influence of supplementary cementitious materials (SCM) in combination with ordinary Portland cement (OPC) on the rheological properties of fresh paste with and without the effect of superplasticizers. Yield stress, plastic viscosity and storage modulus are the rheological parameters which were evaluated for all the design mixtures to fundamentally understand the synergistic effects of the SCM. A time-dependent study was conducted on these blends to explore the structure formation at various time intervals which explains the effect of hydration in conjecture to its physical stiffening. The second phase focuses on the rheological characterization of novel iron powder based binder system. The results of this work indicate that the rheological characteristics of cementitious suspensions are complex, and strongly dependent on several key parameters including: the solid loading, inter-particle forces, shape of the particle, particle size distribution of the particles, and rheological nature of the media in which the particles are suspended. Chemical composition and reactivity of the material play an important role in the time-dependent rheological study. A stress plateau method is utilized for the determination of rheological properties of concentrated suspensions, as it better predicts the apparent yield stress and is shown to correlate well with other viscoelastic properties of the suspensions. Plastic viscosity is obtained by calculating the slope of the stress-strain rate curve of ramp down values of shear rates. In oscillatory stress measurements the plateau obtained within the linear visco-elastic region was considered to be the value for storage modulus. Between the different types of fly ash, class F fly ash indicated a reduction in the rheological parameters as opposed to class C fly ash that is attributable to the enhanced ettringite formation in the latter. Use of superplasticizer led to a huge influence on yield stress and storage modulus of the paste due to the steric hindrance effect. In the study of iron based binder systems, metakaolin had comparatively higher influence than fly ash on the rheology due to its tendency to agglomerate as opposed to the ball bearing effect observed in the latter. Iron increment above 60% resulted in a decrease in all the parameters of rheology discussed in this thesis. In the OPC-iron binder, the iron behaved as reinforcements yielding higher yield stress and plastic viscosity. / Dissertation/Thesis / Masters Thesis Civil Engineering 2016

abstract: Sustainable materials and methods have achieved a pivotal role in the research plethora of the new age due to global warming. Cement production is responsible in contributing to 5% of global CO2 emissions. Complete replacement of cement by alkaline activation of aluminosilicate waste materials such as slag and fly ash is a major advancement towards reducing the adverse impacts of cement production. Comprehensive research has been done, to understand the optimized composition and hydration products. The focus of this dissertation is to understand the multiscale behavior ranging from early age properties, fundamental material structure, fracture and crack resistance properties, durability responses and alternative activation methods to existing process. The utilization of these materials has relied primarily on the dual benefits of reduced presence in landfills and cost. These have also proven to yield a higher service life as opposed to conventional ordinary portland cement (OPC) concrete due to an enhanced microstructure. The use of such materials however has not been readily acceptable due to detrimental early age behavior. The influence of design factors is studied to understand the reaction mechanism. Silicon polymerization at the molecular level is studied to understand the aluminosilicate interactions which are responsible for prevention of any leaching of ions. A comparative study between fly ash and slag binders is carried out to evaluate the stable states of sodium, aluminum and silicon in both these binders, since the likelihood of the sodium ions leaching out is high. Compressive and flexural strength have been reported in previous literature, but the impact of crack resistance was unevaluated from an approach of characterizing the fracture process zone. Alternative routes of activation are explored with an intent to reduce the high alkalinity by use of neutral salts such as sodium sulfate. High volume OPC replacement by both class C and F fly ash is performed to evaluate the differences in hydration phase formation responsible for its pore refinement and strength. Spectroscopic studies have also allowed to study the fundamental material structure. Durability studies are also performed on these samples to understand the probability external sulfate attacks as opposed to OPC mixes. / Dissertation/Thesis / Doctoral Dissertation Engineering 2016

Made available in DSpace on 2014-10-09T12:35:41Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:03:55Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:33:31Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:36Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP