Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-07-06T13:50:36Z No. of bitstreams: 1 CARLOS THIAGO CÂNDIDO CUNHA - TESE (PPGCEMat) 2015.pdf: 3145702 bytes, checksum: bad9f1c620f682b0e77a37c797d9bc37 (MD5) / Made available in DSpace on 2018-07-06T13:50:36Z (GMT). No. of bitstreams: 1 CARLOS THIAGO CÂNDIDO CUNHA - TESE (PPGCEMat) 2015.pdf: 3145702 bytes, checksum: bad9f1c620f682b0e77a37c797d9bc37 (MD5) Previous issue date: 2015-06-22 / Capes / O hidróxido de sódio (NaOH) e o cloro estão entres os produtos químicos mais importantes na indústria e são produzidos simultaneamente pela eletrólise da salmoura. As células eletrolíticas são compostas de uma câmara catódica e uma anódica, separadas por um diafragma que permite a passagem dos íons por migração iônica. A maioria dos diafragmas se utilizam de amianto e as leis ambientais vigentes direcionam para extinção ou substituição deste material. Assim, foi realizado um estudo sobre o desenvolvimento de diafragmas alternativos à base de materiais poliméricos e aditivos que pudessem substituir o amianto e possibilitassem sua aplicação na indústria de cloro-soda. Para tanto, empregou-se fibras poliméricas, a exemplo do Polietileno de Ultra Alto Peso Molecular (PEUAPM), que resiste as condições severas do processo eletrolítico. Também se fez necessário o emprego da dopagem com carga inorgânica (argilas) para conferir menor permeabilidade aos diafragmas. Diante disso, foram desenvolvidos sistemas para deposição e caracterização dos diafragmas que possibilitam a reprodutividade e análises adequadas comparadas ao âmbito industrial. Partindo de um planejamento experimental de misturas com 5 diferentes fibras pode-se avaliar qual composição de diafragma favoreceu melhores resultados nos parâmetros da eletrólise. Os resultados se mostraram promissores, tendo em vista que dentre as 15 formulações testadas conseguiu-se chegar a uma composição cujas propriedades eletroquímicas atendem todas as especificações podendo inclusive ser aplicado em escala industrial. / Sodium hydroxide (NaOH) and chlorine are among the most important chemicals in industry and are produced simultaneously by the electrolysis of brine. Electrolyte cells are consisted by a cathodic and anodic chamber, separated by a diaphragm that allows the passage of ions by ion migration. Most diaphragms using asbestos and environmental laws in use direct to extinction or replacement of this material. In this way, it was done a study on the development of alternative diaphragm based on polymeric materials and additives that could replace the asbestos and could allow its application in chlorine-soda industry. So, polymeric fibres was used, such as, Ultra High Molecular Weight polyethylene (UHMWPE), resisting the harsh conditions of the electrolytic process. Also it was studied the use of doping with inorganic fillers (clays) to provide less permeability to the diaphragms. For this, systems were developed for deposition and characterization of diaphragms that make it possible the reproducibility and suitable analysis compared to the industrial scope. Starting from experimental planning of mixtures with 5 different fibers, it was evaluated which composition of diaphragm given best results in the electrolysis parameters. The results were promising, considering that among the 15 formulations, it was reached a composition whose electrochemical properties meet all specifications and can even be applied on an industrial scale.

In blast furnace ironmaking one major challenge is to control and measure the alkalis circulating and accumulating in the blast furnace (BF). Alkali enter the BF with the primary raw material and will form a cycle where it is first reduced to metal at the lower parts forming gas. Alkali then follows the gas flow up where it oxidizes and solidies as the oxide form has a higher melting and volatilization temperature. Condensation then occurs on burden material and in their pores and by that it is following the burden downwards. The circular nature of the reactions leads to a build-up of alkali in the form of potassium in the BF that is hard to control or measure. Condensation of alkali compounds can also occur on the BF walls functioning like a glue to which particles attach, forming scaffolds that can rapidly increase and disturb the burden descent. The increased alkali catalyzes gasication of coke with CO2 that increasescoke consumption and leads to disintegration of coke. A common method today to control alkali is by varying the basicity in the BF. As lower basicity increases the amount alkali removed through slag while at the same time reducing the amount of sulfur that can be removed with the slag. This project was divided into two parts. The first part was a continuation of a previous study performed at Swerea MEFOS. Where to control the effect of alkali on coke gasication a method was tested using coke ash modication to inhibit the catalyzing properties of alkali bound on coke. The method has previously shown that alkalis are bound in the desired form but the added amount was not sufficient for inhibition of all picked-up alkalis. In this study, additional trials with higher additions of kaolin was performed. 2 wt% kaolin was added to the coal blend for producing coke that was then added to LKAB's experimental blast furnace (EBF) as basket samples in the end of a campaign. The excavated samples were analyzed using XRF, XRD, SEM-EDS and TGA to find if the alkali was bound in aluminum silicates in the coke ash, if the addition was sufficient for binding all alkalis and if the catalytic effect in coke gasication had been achieved. The second part was a novel approach with a statistical process analysis using SIMCA to connect top gas composition of SSAB Oxelösund's BF No. 4 to alkali content using process data. The approach investigated the correlation between NH3(g) and HCN(g) in the top gas to alkali content. Expanding on the possibility to measure alkali content quickly for the operators using top gas measurements. Top gas composition was measured using a mass spectrometer (MS) and where complimented with process and tap data provided by SSAB. Data was analyzed using the multivariate analysis tool SIMCA 15 to find possible correlations. Results from the first part showed that the alkali that was found was present as alkali aluminum silicates independent of kaolin addition after the EBF. As temperature along gas composition was the main factors behind alkali uptake in coke. Main differences in alkali uptake and development of coke properties in the BF was linked to the temperature and gas composition profile during tests campaigns compared. Results from TGA showed that the reaction rate of coke with CO2 increases with increasing K2O and that start of reaction was lower with increasing alkali. The results from the second approach did not find a correlation between HCN(g) and K2O in slag. Positive correlation could be seen between HCN(g) and increased SiO2 in slag and that H2O(g) would affect HCN(g) negatively.

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

A reação álcali-agregado é uma patologia do concreto conhecida há mais de 60 anos no meio técnico, e envolve os álcalis, provenientes em maior parte do cimento, e certos constituintes mineralógicos dos agregados. O produto desta reação é um gel higroscópico, que, em contato com a água, aumenta de volume consideravelmente. Os danos decorrentes da reação envolvem principalmente o desenvolvimento de um quadro de fissuração intenso, o que acarreta outras diversas manifestações patológicas, e movimentações de peças estruturais. Os relatos mais freqüentes de ocorrência da reação sempre foram em estruturas hidráulicas, tais como as barragens, em função do permanente contato com a água. Entretanto, nos últimos anos, diversos outros tipos de estruturas têm sido afetados, inclusive fundações de edificios, deixando o problema em evidência. O único modo de combater a reação é prevení-la através do uso de adições minerais, e para tal se faz necessário avaliar o agregado em questão, dispondo de um método de ensaio confiável. Este trabalho buscou analisar um dos métodos de ensaio mais utilizados no mundo todo para avaliar a reação álcali-agregado, a ASTM C 1260. Foram modificados alguns parâmetros de moldagem para verificar a influência destes nos resultados de expansão fornecidos pelo ensaio. Avaliaram-se os fatores: relação água/cimento, consistência da argamassa e forma do grão de agregado, e no total foram conduzidos 63 diferentes ensaios de expansão para analisar a influência destes fatores. Ensaios auxiliares foram realizados para justificar os resultados, e utilizou-se tratamento estatístico para verificação da validade dos mesmos. Foi observado que a forma de britagem do agregado, para posterior realização do ensaio, interfere diretamente nas condições de moldagem. E, o mais importante: isto resulta em expansões diferenciadas na idade de avaliação do agregado. Para evitar classificações errôneas de agregados através do uso da ASTM C 1260, uma norma usada em vários países, sugere-se que sejam fixados o maior número possível de parâmetros de moldagem. / The alkali-aggregate reaction 1s a concrete pathology known for more than 60 years, involving the alkalis (mostly from the cement), and some mineralogical components of the aggregates. The product o f this reaction is a hygroscopic gel that, in contact with water, has its volume greatly increased. The damage resulting from this reaction is mainly a situation of intense craking, which causes other pathological manifestations and movements of the structure. The most frequent reports o f this reaction have always been in hydraulic structures, such as dams, caused by the permanent contact with water. However, in the last few years, many other kinds of structures have been affected, including building foundations; which brought the problem to international evidence. The only way to prevent the expansion caused by the reaction is the use o f mineral admixtures as a substitute o f part o f the cement content, but first it is necessary to evaluate the aggregate in use, with a satisfactory test method. This work' s purpose is to analyze one o f the test methods commonly used throughout the world to evaluate the alkali-aggregate reaction, the ASTM C 1260. Some molding parameters have been modified so as to check their influence on the results of expansion obtained through this test. These factors have been evaluated: water/cement ratio, mortar consistency and shape of the aggregate particle. A total of 63 different tests of expansion were conducted to evaluate their influence. Additional tests were done so as to justify the results, and statistical analysis was used to validate the results. It was observe that the way the aggregate is crushed, for subsequent execution of the test, directly interferes in the conditions of molding. And, the most important: the way the aggregate is crushed results in different expansions and it is increased with the age of the evaluation of the test. To prevent a erroneous classification o f the aggregates through the use of ASTM C 1260, a standard used in many countries, it is suggested that test conditions should be better defined.

A reação química entre os hidróxidos alcalinos presentes no cimento e fases minerais reativas presentes no agregado dá origem a um gel sílico-alcalino que ao adsorver água se expande, podendo causar expansão e fissuração do concreto, afetando a sua durabilidade. Este fenômeno é chamado de reação álcali-agregado (RAA) e embora seja conhecido há aproximadamente 70 anos no meio técnico, e principalmente estar relacionado às grandes barragens e estruturas de concretos diversas de Usina hidrelétricas, nos últimos anos outros tipos de estruturas têm sido afetadas, inclusive fundações de edifícios, deixando ainda mais o problema em evidência. As medidas preventivas para esta reação já são conhecidas há muito tempo e aplicadas rotineiramente em estruturas de usinas hidrelétricas quando se tem agregados reativos, sendo recentemente normalizadas no Brasil. Porém, ainda existem grandes carências em se combater o fenômeno quando já se encontra instalado no concreto. Diante do exposto, este trabalho, desenvolvido dentro do programa de P&D de Furnas/ANEEL, teve como principal objetivo verificar a potencialidade de compostos a base de Silanos através de testes laboratoriais com vistas à aplicação em concretos contendo agregados reativos na tentativa de minimizar as expansões residuais em estruturas que já se encontram afetadas. As atividades desenvolvidas contemplam ensaios em barras de argamassas que foram tratadas, em três etapas distintas, com compostos a base de silanos. A primeira etapa foi desenvolvida como projeto piloto, e seus resultados serviram de apoio para a realização das etapas seguintes. Nas segunda e terceira etapas foi verificada a atuação dos produtos na prevenção e na mitigação da RAA, respectivamente. Os resultados obtidos na primeira etapa não foram satisfatórios, pois as expansões foram maiores do que as da referência. Já para a segunda e terceira etapas, os procedimentos para aplicação dos tratamentos previram que as barras fossem tratadas sem que estivessem previamente expostas à solução de NaOH, conforme realizado na primeira etapa, o que possivelmente ocasionou o acréscimo das expansões, sem a eficiência do produto. Os resultados obtidos nessas etapas se mostraram eficientes tanto na prevenção quanto na mitigação das expansões residuais da RAA e, embora o lítio produza uma maior eficiência na redução das expansões, os tratamentos à base de silano, e principalmente do tipo octiltrietoxisilano, mostraram muito promissores. Após o lítio, o tratamento à base do silano OCTEO, no teor de 10%, com o surfactante tipo DMSO, em aplicação múltipla, se mostrou mais eficiente. Para complemento da parte experimental da pesquisa, foram realizados ensaios de absorção de água por imersão e análises por microscopia eletrônica de varredura e verificou-se o efeito dos produtos de tratamento nos poros das argamassas. / The chemical reaction between cement alkaline hydroxides and reactive silica present in some aggregates produces an alkaline silicate gel that expands when it adsorbs water and can cause concrete expansion and cracking, thereby affecting durability. This phenomenon is known as alkali-aggregate reaction (AAR) and was first detected over 70 years ago as the cause of deterioration especially in large dams and a number of other concrete structures in hydroelectric power plants in general. In recent years, AAR has also been noted in other types of structure, such as building foundations, bringing the problem more dramatically to the fore. Preventive measures for AAR have long been known and are routinely applied in hydroelectric power plant structures when there are reactive aggregates. These measures have been recently standardized in Brazil. Nevertheless there are still flaws in our knowledge regarding how to mitigate expansion when this phenomenon is already present in the concrete. Considering these aspects, the main purpose of this study, developed within Furnas/ANEEL Research and Development Program, is to verify, at laboratory level, the mitigating potential of silane compounds in residual expansion in affected mortars which contain reactive aggregates. Assays were performed on bars of mortar treated with silane compounds in three different stages. The first stage was developed as a pilot study with results serving as support for the following stages. The second and third stages verified the activity of the products in the prevention and mitigation of AAR, respectively. The results obtained in the first stage were unsatisfactory as the expansions were greater than the references. The second and third stage treatments required bars not previously exposed to NaOH, differently from the first stage and which may have been the cause of the increased expansion and product inefficiency. The results in these stages proved satisfactory both in preventing and mitigating AAR residual expansions, and although lithium is more efficient in reducing expansions, silane based treatments, mainly the octyltriethoxysilane types proved most promising. Following lithium, the most efficient treatment was 10% content OCTEO silane with a DMSO type surfactant applied in multiple layers. To complement the experimental part of the study, assays on water absorption through immersion were performed as well as scanning electron microscopy to verify the effect of the treatment products on the mortar pores.

Made available in DSpace on 2014-06-11T19:25:21Z (GMT). No. of bitstreams: 0 Previous issue date: 2007-10-29Bitstream added on 2014-06-13T19:12:01Z : No. of bitstreams: 1 silva_djf_me_ilha.pdf: 2179863 bytes, checksum: 355cf90186323e4d66dfc92b04ecf1cc (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Várias pesquisas realizadas com compostos a base de lítio tem mostrado resultados satisfatórios na redução da expansão associada à reação álcali-sílica (RAS), mas ainda existem muitas dúvidas sobre seus mecanismos de ação. A presente pesquisa avaliou os efeitos de uma adição química a base de nitrato de lítio (LiNO3) na redução da expansão associada a RAS, utilizando várias dosagens. Os estudo dos efeitos do LiNO3 na RAS foi feito pelo método acelerado das barras de argamassa (ASTM C-1260) utilizando dois tipos de agregado reativo. Também foram realizados ensaios de expansão com uma adição mineral a base de cinza volante a fim de correlacionar os efeitos de uma adição mineral com uma química na redução da expansão devido a RAS. Ensaios de resistência à compressão e trabalhabilidade foram realizados também buscando algum efeito do LiNO3 nestas propriedades. Os resultados do ensaio ASTM C-1260 indicaram que as adições de lítio foram efetivas na redução da expansão para os dois tipos de agregados reativos, sendo que para as condições e materiais utilizados na presente pesquisa foi necessário uma de adição de LiNO3 com relação molar (Li2O/Na2Oeq) de 7,00 para reduzir a expansão ao valor aceitável pela norma de 0,10% aos 16 dias. Foi observado também intensidades de redução da expansão diferentes entre os dois tipos de agregados estudados devido a diferença de reatividade dos mesmos. Verificou-se um limite de adição de lítio para o basalto, onde não havia mais redução significativa de expansão com o aumento da dosagem de adição. Observou-se também que as misturas contendo LiNO3 reduziram a expansão ao longo dos 30 dias, enquanto nas misturas contendo FA a expansão continuou a aumentar ao longo do teste. Os ensaios de condição de trabalhabilidade e de resistência à compressão mostraram que o LiNO3 não afeta consideravelmente estas propriedades. / Lithium compounds have been shown satisfactory results for the reduction of the expansion due to alkali-silica reaction (ASR), but there are many doubts about its mechanisms of action. The present research evaluated the effects of a chemical addition to lithium nitrate based (LiNO3) on the reduction of expansion associated with ASR, utilizing several dosages. For the study of the effects of the LiNO3 on the ASR it was used the accelerated mortar bar method (ASTM C-1260), with two kinds of reactivate aggregate. Mortar bars were molded also with a mineral addition of fly ash based (FA) with the objective to compare the effects of a mineral addition with a chemistry on the expansion due ASR. Compressive strength and consistence index tests had been carried also for searching some effects of the LiNO3 at these properties. The results from ASTM C-1260 showed that the addition of LiNO3 were effective on the expansion reduction for two kinds of reactive aggregate, which current conditions and materials on this research required a LiNO3 addition with (Li/Naeq) of 7,00 molar ratio to decrease the expansion to an acceptable value of 0,10% on 16 days. Also, the intensity of the expansion reduction was observed between two kinds of studied aggregates by their reactivity difference. A lithium additive upper bound was verified for the basalt, where it did not have more significant reduction of expansion with the increase of the dosage of addition. Also, was observed that admixtures that contained LiNO3 have reduced the expansion trough 30 days, while on the admixtures that contained FA the expansion grew up. The results obtained for the compressive strength and consistence index tests showed no significant differences between mixtures with and without LiNO3 admixture.

A reação química entre os hidróxidos alcalinos presentes no cimento e fases minerais reativas presentes no agregado dá origem a um gel sílico-alcalino que ao adsorver água se expande, podendo causar expansão e fissuração do concreto, afetando a sua durabilidade. Este fenômeno é chamado de reação álcali-agregado (RAA) e embora seja conhecido há aproximadamente 70 anos no meio técnico, e principalmente estar relacionado às grandes barragens e estruturas de concretos diversas de Usina hidrelétricas, nos últimos anos outros tipos de estruturas têm sido afetadas, inclusive fundações de edifícios, deixando ainda mais o problema em evidência. As medidas preventivas para esta reação já são conhecidas há muito tempo e aplicadas rotineiramente em estruturas de usinas hidrelétricas quando se tem agregados reativos, sendo recentemente normalizadas no Brasil. Porém, ainda existem grandes carências em se combater o fenômeno quando já se encontra instalado no concreto. Diante do exposto, este trabalho, desenvolvido dentro do programa de P&D de Furnas/ANEEL, teve como principal objetivo verificar a potencialidade de compostos a base de Silanos através de testes laboratoriais com vistas à aplicação em concretos contendo agregados reativos na tentativa de minimizar as expansões residuais em estruturas que já se encontram afetadas. As atividades desenvolvidas contemplam ensaios em barras de argamassas que foram tratadas, em três etapas distintas, com compostos a base de silanos. A primeira etapa foi desenvolvida como projeto piloto, e seus resultados serviram de apoio para a realização das etapas seguintes. Nas segunda e terceira etapas foi verificada a atuação dos produtos na prevenção e na mitigação da RAA, respectivamente. Os resultados obtidos na primeira etapa não foram satisfatórios, pois as expansões foram maiores do que as da referência. Já para a segunda e terceira etapas, os procedimentos para aplicação dos tratamentos previram que as barras fossem tratadas sem que estivessem previamente expostas à solução de NaOH, conforme realizado na primeira etapa, o que possivelmente ocasionou o acréscimo das expansões, sem a eficiência do produto. Os resultados obtidos nessas etapas se mostraram eficientes tanto na prevenção quanto na mitigação das expansões residuais da RAA e, embora o lítio produza uma maior eficiência na redução das expansões, os tratamentos à base de silano, e principalmente do tipo octiltrietoxisilano, mostraram muito promissores. Após o lítio, o tratamento à base do silano OCTEO, no teor de 10%, com o surfactante tipo DMSO, em aplicação múltipla, se mostrou mais eficiente. Para complemento da parte experimental da pesquisa, foram realizados ensaios de absorção de água por imersão e análises por microscopia eletrônica de varredura e verificou-se o efeito dos produtos de tratamento nos poros das argamassas. / The chemical reaction between cement alkaline hydroxides and reactive silica present in some aggregates produces an alkaline silicate gel that expands when it adsorbs water and can cause concrete expansion and cracking, thereby affecting durability. This phenomenon is known as alkali-aggregate reaction (AAR) and was first detected over 70 years ago as the cause of deterioration especially in large dams and a number of other concrete structures in hydroelectric power plants in general. In recent years, AAR has also been noted in other types of structure, such as building foundations, bringing the problem more dramatically to the fore. Preventive measures for AAR have long been known and are routinely applied in hydroelectric power plant structures when there are reactive aggregates. These measures have been recently standardized in Brazil. Nevertheless there are still flaws in our knowledge regarding how to mitigate expansion when this phenomenon is already present in the concrete. Considering these aspects, the main purpose of this study, developed within Furnas/ANEEL Research and Development Program, is to verify, at laboratory level, the mitigating potential of silane compounds in residual expansion in affected mortars which contain reactive aggregates. Assays were performed on bars of mortar treated with silane compounds in three different stages. The first stage was developed as a pilot study with results serving as support for the following stages. The second and third stages verified the activity of the products in the prevention and mitigation of AAR, respectively. The results obtained in the first stage were unsatisfactory as the expansions were greater than the references. The second and third stage treatments required bars not previously exposed to NaOH, differently from the first stage and which may have been the cause of the increased expansion and product inefficiency. The results in these stages proved satisfactory both in preventing and mitigating AAR residual expansions, and although lithium is more efficient in reducing expansions, silane based treatments, mainly the octyltriethoxysilane types proved most promising. Following lithium, the most efficient treatment was 10% content OCTEO silane with a DMSO type surfactant applied in multiple layers. To complement the experimental part of the study, assays on water absorption through immersion were performed as well as scanning electron microscopy to verify the effect of the treatment products on the mortar pores.

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

Alkali-soluble resins (ASRs) were prepared by (i) solution and (ii) emulsion polymerization. All ASRs were synthesized with number-average molar masses < 20,000 g mol-1 and all had 15 wt% methacrylic acid 5 wt% styrene, the remaining 80 wt% was composed of either methyl methacrylate or a combination of methyl methacrylate and ethyl acrylate. All emulsion ASRs were made to 20% solids, with volume-average particle diameters (dv) in the region 30 – 50 nm, with a glass transition temperature of 80 – 120 °C. Emulsion polymerization was the preferred route for ASR synthesis, to allow further studies on their dissolution behaviour. Before their use as colloidal stabilizers, the dissolution behaviour of the ASRs needed to beinvestigated e.g. effect of temperature, molar mass, and composition. Particle size and absorbance measurements were taken during dissolution of ASRs to achieve 100%neutralization and these were shown to have two stages, an apparent particle swelling (whichwas rapid), and a slower, decrease in particle size as water-soluble polymeric material wasdiffusing out of the ASR particles. From this, further interpretation allowed for calculating the diffusion coefficient of the ASR polymer using the Stokes-Einstein equation. Time-domain nuclear magnetic resonance (TD-NMR) was employed to enhance understanding of what is occurring in the ASR particles, and in the aqueous, continuous phase. The final aspect of this project was to use the ASRs prepared as colloidal stabilizers in emulsion polymerizations of butyl acrylate (BA) and butyl methacrylate (BMA) using varying levels and also the effect of adding additional surfactant. The results show that the effect of ASR molar mass, the concentration of stabilizer, and also the impact of the EA-containing ASR greatly influence stability, whereby lower ASR molar mass, higher levels of stabilizer and including EA greatly benefit colloidal stability in PBA latexes. In PBMA latexes, a similar trend was also observed, but, the presence of ethyl acrylate (EA) in the ASR backbone has a detrimental effect on the colloidal stability, caused by the inability of grafting to occur between the ASR and PBMA.

Orientador: Mauro Dal Secco de Oliveira / Banca: Ricardo Andrade Reis / Banca: Jane Maria Bertocco Ezequiel / Banca: Selma de Fátima Grossi / Banca: Ricardo Dias Signoretti / Resumo: Objetivou-se com este estudo avaliar o valor nutritivo da cana-de-açúcar na alimentação de bovinos. Foram avaliados as variáveis correlacionados com a estabilidade aeróbia, pH microrganismos, composição bromatológica, teores de macro, microminerais, metais tóxicos, digestibilidade, ganho de peso e consumo. Para análise estatística do consumo e ganho de peso foi utilizado delineamento inteiramente casualizado com quatro repetições por tratamento, a análise estatítica das demais variáveis foi feita utilizando o delineamento inteiramente casualizado, em esquema de parcelas subdivididas, sendo as doses de cal alocados nas parcelas (0; 0,5; 1,0; 1,5 e 2,0 %) e os tempos de exposição ao ar nas subparcelas (0, 24, 48, 72 e 96 horas), com quatro repetições por tratamento. As médias em ambos os casos foram comparadas utilizando-se o teste de Tukey ao nível de 5 % de probabilidade. Foi encontrado efeito significativo para todas as variáveis estudas com exceção daquelas relacionadas ao desempenho e consumo. A cal virgem foi capaz de aumentar a estabilidade aeróbia e controlar o desenvolvimento dos microrganismos (leveduras principalmente), solubilizar a fração fibrosa da cana e aumentar a digestibilidade, porém estes efeitos não ocasionaram um maior consumo nem maior desempenho dos animais alimentados com este volumoso, indicando que outros fatores podem estar influenciando no desempenho dos animais. Com o passar das horas a cana-de-açúcar diminui o seu valor nutritivo porém esta diminuição é menor para os tratamentos que continham a cana-de-açúcar tratada com cal virgem. / Abstract: This study objective was evaluete sugar cane nutritional value of in cattle feeding. Variables correlated were evaluated with aerobic stability, pH microorganisms, bromatologic composition, levels of macro, microminerals, toxic metals, digestibility, weight gain and consumption. For consumption and weight gain statistical analysis a randomized design with four replicates per treatment was used, analysis statistical for other variables were made using randomized design in a split-plot, and the doses of lime allocated in pieces (0 , 0.5, 1.0, 1.5 and 2.0%) and the time of exposure to air the subplots (0, 24, 48, 72 and 96 hours), with four replicates per treatment. The averages in both cases were compared using the Tukey test at 5% level of probability. Significant effect was found for all the variables studied except those related to the performance and consumption. The lime was able to increase aerobic stability and control the microorganisms (mainly yeasts) development, solubilizing cane fibrous fraction cane and increasing digestibility, but these effects do not lead to higher consumption and higher performance of animals fed with forage, indicating that other factors may be influencing animals performance. With the passing of the hours the sugar cane diminish their nutritional value but this reduction is lower for the treatments that contained the sugar cane treated with lime. / Doutor