The aim of this master thesis is study of possibilities of processing energy by-products, especially coal fly ash and fluidized bed ash, by hydrothermal treatment. Thanks to hydrothermal conditions and proper alkali activation of ashes we can obtain zeolites. Zeolites are microporous crystalline aluminosilicates which are use in many industrial sectors as catalysts, adsorbents and very good ion exchangers. The results of hydrothermal synthesis are influenced by many variable factors. This thesis mainly focused on influence of chosen alkali activator and the concentration of the activator together with a temperature of hydrothermal process. Other factor that is studied is choice of starting materials and solution/ash ratio. Phase composition of prepared samples was characterized by XRD and scanning electron microscopy (SEM). Also cation exchange capacity of prepared samples was determined.

Philosophiae Doctor - PhD / Aqueous ion-intercalation batteries (AIB’s) have the potential to provide both high power for hybrid-electric transport, and low cost bulk energy storage for electric grid supply. However, a major setback to AIB development is the instability of suitable ionintercalation anode material in aqueous electrolyte. To counter this problem, the use of activated carbon (AC) (a supercapacitor anode) paired against the low cost ionintercalation cathode spinel LiMn2O4 (LMO) provides a stable alternative. This thesis comprises two novel areas of investigation concerning: (1) the development of the AC/LMO cell for high power applications, and (2) the introduction of PbSO4 as a high capacity alternative anode material paired against LMO for low cost bulk energy storage. The study on AC/LMO explores the electrode combination’s practical specific energy and power capability at high P/E (power to energy ratio) of 50:1 suitable for hybrid electric vehicle batteries. To study the relationship between electrode material loading density, active material performance, and current collector mass contribution, a specially designed cell was constructed for galvanic cycling of different thicknesses of electrode. Between a loading density range of 25 – 100 mg, ~50 mg of total active material between two 1 cm2 current collectors produced the highest 50:1 P/E ratio values of 4 Wh/kg and 200 W/kg, constituting a 4-fold reduction of the active material values of thin films at 50:1 P/E. The cycling potentials of the individual electrodes revealed that doublings of electrode film loading density increased the LMO electrode’s polarization and voltage drop to similar levels as doublings in applied current density. However, by increasing the charging voltage from 1.8 V to 2.2 V, 6 Wh/kg and 300 W/kg was obtainable with minimal loss of energy efficiency. Finally a large-format cell of a calculated 3 Ah capacity at 50:1 P/E was constructed and tested. The cell produced ~60% of the anticipated capacity due to a suspected high level of resistance in the electrode contact points. The overall conclusion to the study was that AC/LMO holds promise for high power applications, and that future use of higher rate capability forms of LMO offers a promising avenue for further research. v The second part of this thesis presents the development of a novel cell chemistry, PbSO4/LMO, that has yet to be reported elsewhere in existing literature. The cell uses aqueous pH 7, 1 M, Li2SO4 electrolyte, and forms an electrode coupling where the PbSO4 anode charge/discharge is analogous to that in Pb-acid batteries. The average discharge voltage of the cell was 1.4 V and formed a flat charge/discharge plateau. The use of a low cost carbon coating method to encapsulate PbSO4 microparticles had a marked improvement on cell performance, and compared to uncoated PbSO4 improved both rate capability and specific capacity of the material. The active materials of the carbon-coated PbSO4/LMO cell produced a specific energy 51.1 Wh/kg, which, if a 65% yield is possible for a practical cell format, equals 38.4 Wh/kg, which is 15 Wh/kg higher than AC/LMO bulk storage cells at 23 Wh/kg, but lower than Pb-acid batteries at ~25-50 Wh/kg. Interestingly, the specific capacity of PbSO4 was 76 mAh/g compared to 100 mAh/g in Pb-acid cells. The predicted cost of the cell, providing a 65% value of the active material specific energy for a practical cell can be realized, is on par with Pb-acid battery technology and, importantly, uses 2.3 × less Pb/kWh. The cycling stability achieved thus far is promising, but will require testing over comparable cycle life periods to commercial batteries, which could be anywhere between 5 – 15 years.

L’intercalation de métaux dans le graphite a été réalisée pour la première fois en 1926. Depuis cette découverte, de nombreux composés binaires et ternaires ont été synthétisés. Au cours de ce travail, la méthode solide-liquide en milieu alliage fondu à base d’alcalin a d’abord été utilisée afin d’intercaler l’or dans le graphite à l’aide du potassium. Puis, l’intercalation du calcium dans des matériaux B-C-N de structure graphitique a été réalisée par le biais du lithium. La diffraction des rayons X, l’analyse par faisceau d’ions, la microscopie électronique ainsi que les techniques spectroscopiques associées ont été mises en œuvre pour caractériser ces nouveaux composés. Dans le cas du système graphite-potassium-or, trois nouveaux composés ternaires de premier stade et de distances interplanaires très différentes (1311, 953 et 500 pm) ont pu être synthétisés. Le composé K1,3Au1,5C4 a été isolé de façon reproductible et présente selon l’axe c une séquence d’empilement K-Au-Au-Au-K pour l’insérat. L’étude du mécanisme d’intercalation menant à ce composé a mis en évidence un intermédiaire réactionnel de formule K1,6Au0,7C4 dont le feuillet inséré est tricouche. Le troisième composé, KAu0,7C4, constitué de deux couches mixtes or-potassium, s’est quant à lui révélé métastable. Parallèlement, l’intercalation d’un alliage Li-Ca dans le matériau B-C-N a été réalisée avec succès. L’analyse par faisceau d’ions de l’hôte a permis de doser sur un même échantillon la teneur en bore, carbone et azote, conduisant à une formule B2C5N. Les mesures effectuées sur le matériau intercalé montrent la préservation du réseau hôte et l’insertion de 0,6 atome de lithium par atome de calcium / Since the discovery in 1926 of the first graphite intercalation compounds containing alkali metals, numerous binary and ternary compounds have been synthesized. In this work, solid-liquid method in alkali metal based molten alloys has been employed to intercalate gold into graphite using potassium as an intercalation vector for opening the van der Waals’s gaps and decreasing the reaction temperature. Then, lithium has been used to assist the intercalation of calcium into B-C-N compounds. X-ray diffraction, ion beam analysis, electron microscopy and associated spectroscopy techniques have been performed to characterize the as-prepared compounds. In the case of graphite-potassium-gold system, three novel ternary first stage intercalation compounds with very different repeat distances (1311, 953 and 500 pm) have been synthesized. The K1.3Au1.5C4 compound, isolated in a reproducible fashion, presents a K-Au-Au-Au-K c-axis stacking sequence for the intercalated sheets. The study of its intercalation mechanism evidenced an intermediate product which chemical formula is K1.6Au0.7C4, with three-layered intercalated sheets. The third compound KAu0.7C4 is metastable and contains in each van der Waals‘s gap two successive layers containing a mixture of gold and potassium. Elsewhere, the intercalation of a Li-Ca alloy into B-C-N host material has been successfully carried out. The ion beam analysis of the pristine B-C-N lead to determine on a same sample the amount of boron, carbon and nitrogen with the corresponding B2C5N formula. The experiments realized on the intercalated compound showed the preservation of the host lattice and the intercalation of 0.6 lithium per calcium atom

Made available in DSpace on 2017-06-01T17:57:19Z (GMT). No. of bitstreams: 1 Geovani_confrontado.pdf: 11502780 bytes, checksum: 5d0ce88d9f0d752b9854a355ea8bb142 (MD5) Previous issue date: 2007-08-15 / The alkali-aggregate reaction affects the durability and the mechanical resistance of the concrete structures, provoking cracks in the structural elements. Despite of these pathological manifestations, it cannot affirm that, even so the reaction is slow, the ultimate limit state cannot be reached. The occurrence of this phenomenon on blocks foundation is rarely described in literature. Recently was identified in foundations of buildings in the Metropolitan of Recife Region, constituting a problem that comes calling the attention of the community technique and the productive sector of civil construction. The pile caps affected by the AAR must suffer interventions with adequate techniques of recovery to each situation. Inside of that focus, this work presents the results of the attendance of the services of microcement injection in cracks in the blocks of a building in recovery process. It still presents the reinforcement proposal for the pieces of infrastructure affected by expansible reaction. To go accomplished extractions of specimens, cleaning and superficial closing of the cracks with an epoxy mixture and kaolin, application of the microcement inside the cracks and extraction of specimens after the injection for verification of the effectiveness of the fulfillment of the cracks with the injected material. The results can supply important subsidies for repair pile caps damaged for the action of AAR / A reação álcali-agregado afeta a durabilidade e a resistência mecânica das estruturas de concreto, provocando trincas nos elementos estruturais. Apesar das manifestações patológicas provocadas, não se pode afirmar que, embora a reação seja lenta, o estado limite de ruptura não possa ser atingido. A ocorrência desse fenômeno em blocos de fundação é raramente descrita na literatura. Recentemente foi identificada em fundações de edifícios na Região Metropolitana do Recife, constituindo um problema que vem chamando a atenção da comunidade técnica e do setor produtivo da construção civil. Os blocos de coroamento afetados pela RAA devem sofrer intervenções com técnicas de recuperação adequadas a cada situação. Dentro desse enfoque, este trabalho apresenta os resultados do acompanhamento dos serviços de injeção de microcimento em fissuras nos blocos de uma obra em processo de recuperação. Apresenta ainda a proposta de reforço para as peças de infra-estrutura afetadas pela reação expansiva. Foram realizadas extrações de testemunhos, limpeza e fechamento superficial das fissuras com uma mistura de epóxi e caulim, aplicação do microcimento no interior das trincas e extração de testemunhos após a injeção para verificação da efetividade do preenchimento das fissuras com o material injetado. Os resultados poderão fornecer importantes subsídios para reparo de blocos de coroamento danificados pela ação da RAA.

Made available in DSpace on 2017-06-01T17:57:26Z (GMT). No. of bitstreams: 1 dissertacao_eduardo_alves.pdf: 4097097 bytes, checksum: 9ad4af0b76785acb1b7ae5b0edeb08db (MD5) Previous issue date: 2008-12-01 / The first engineering works reported as being affected by Alkali-Aggregate Reaction (AAR) were pavements and bridges in the state of California - USA, in the 1920's. This diagnosis was proposed by Stanton, T.E., in 1940. From then on, many studies had been presented, supporting that hypothesis. From 1940 to nowadays many other countries, including Brazil had been diagnosing hundreds of cases of AAR in many different types of engineering works, mainly in dams. In Recife, Pernambuco, from the year 2000, many occurrences have been identified as AAR in pile caps. Initially they were observed in the basis of industrial cooling towers and in the pile caps of the Pina Bridge. In 2004, occurred in the neighbor city of Jaboatao the rupture of the Areia Branca Building, a 12 storey, 27 yearold, concrete construction, caused by constructive imperfections in the foundation of the columns. Many people that live in buildings worried much about this fact and asked technical inspections in the foundations. About 30 buildings presented various cracks and the cause is attributed to AAR. Because of the absence of registration of similar cases in the international literature and because the theoretical modelling of the problem is not yet satisfactorily solved, the structural engineers have been presenting intuitive solutions. In this paper four examples of solutions for structural repair of pile caps are showed, using in all of them common procedures, like: cleaning and fulfilling the cracks, addition of steel bars and covering the pile caps with a concrete layer in all surfaces. At the end it is talked about the need to increase the pile caps structural analysis, to verify if the AAR is the only responsible for the fissures in the pile caps, or if there are other associated pathologies / As primeiras obras de engenharia que se tem notícia que foram afetadas pela Reação Álcali-Agregado foram pontes e pavimentos no estado da Califórnia, EUA, nos anos de 1920 a 1930. Este diagnóstico foi proposto por Stanton, T.E., em 1940. A partir daí, vários estudos foram apresentados, dando suporte a essa hipótese. De 1940 até 2008 vários outros países, inclusive o Brasil, diagnosticaram casos de RAA em diversas obras de Engenharia, principalmente em barragens. No Recife, Pernambuco, a partir do ano 2000, várias ocorrências foram diagnosticadas como RAA em blocos de fundação. Inicialmente foram observadas em bases de torres de refrigeração de uma indústria e, posteriormente, nos blocos de fundação da Ponte do Pina. No ano de 2004, houve a ruptura do Edifício Areia Branca, de 12 andares, com 27 anos de idade, na vizinha cidade de Jaboatão, por problemas de falha construtivas nas fundações. Este fato trouxe grande preocupação aos moradores de vários edifícios da região, que passaram a solicitar vistorias técnicas nas fundações dos mesmos. Em cerca de 30 prédios, onde foram observados blocos fissurados, as causas foram atribuídas à RAA. Tendo em vista a falta de registro de casos semelhantes na literatura técnica internacional e que a modelagem teórica do problema ainda não está resolvida satisfatoriamente, tem-se contado com soluções intuitivas dos engenheiros estruturais. Neste trabalho mostram-se quatro exemplos de obras no Recife afetadas pela RAA, detalhando as fases de detecção, diagnóstico, estudos e pesquisas, que resultaram no projeto de soluções para recuperação estrutural dos blocos de fundação, contando com procedimentos que constam, de forma geral, de limpeza e preenchimento das trincas, reforço com armadura suplementar e encamisamento dos blocos. Ao final, chama-se a atenção para a necessidade de evoluir nas análises estruturais dos blocos de fundação, para comprovar se a ação da RAA é a única responsável pelo quadro fissuratório observado nas fundações pesquisadas na Região Metropolitana do Recife, ou se há, porventura, outras patologias associadas

Made available in DSpace on 2017-06-01T17:57:37Z (GMT). No. of bitstreams: 1 joao_ricardo_pereira_silva.pdf: 5270116 bytes, checksum: e2453cbeb125a1529e7873ffe4d87453 (MD5) Previous issue date: 2015-11-25 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Modeling studies the RAA expansion are generally limited by the difficulty due to the heterogeneity and reactive aggregate size range. This work aims to study the issue and help in developing models to predict the potential for expansion of mortar and concrete containing reactive aggregates. The paper presents measurements to provide experimental data on the effect of aggregate size expanding mortar bars. The results show that expansion was measured on mortars relating the standard from 2.4 to 0.15 mm fraction with the individual fractions 2.4; 1.2; 0.6; 0.3; 0.15 mm, where 0.3 mm fraction showed the highest growth and the lowest was the fraction 0.15 mm. You can observe the interference of particle sizes. The effect size of reactive aggregates is evaluated and the consequences of accelerated laboratory tests are discussed. / Os estudos da expansão RAA são geralmente limitados pela dificuldade devido à heterogeneidade e faixa de tamanho de agregados reativos. Este trabalho tem o objetivo de estudar o assunto e ajudar no desenvolvimento de modelos para prever o potencial de expansão da argamassa e do concreto que contém agregados reativos. O trabalho apresenta medições a fim de fornecer dados experimentais sobre o efeito do tamanho do agregado na expansão em barras de argamassa. Os resultados mostram que a expansão medida nas argamassas relacionando a fração padrão 2,4-0,15 mm com as frações individuais 2,4; 1,2; 0,6; 0,3; 0,15 mm, onde a fração 0,6 mm apresentou a maior expansão e a menor foi à fração 0,15 mm. É possível observar a interferência das faixas granulométricas. O efeito do tamanho dos agregados reativos é avaliado e as consequências sobre os ensaios laboratoriais acelerados são discutida.

Concrete has proven to be, by far, one of the most reliable materials for the construction of critical infrastructure. However, despite its structural capacity, concrete members are susceptible to damage mechanisms that may decrease its performance and durability throughout its service life. One such mechanism is alkali-silica reaction (ASR), which takes place when unstable siliceous phases present in coarse or fine aggregates react with the alkali hydroxides from the concrete pore solution, generating a secondary product (i.e., ASR gel); this product swells upon moisture uptake from the surrounding environment, leading to cracking and expansion of the affected concrete. In severe cases of ASR-affected infrastructure, structural safety could become a problem, and thus requiring the demolition of affected members. It is, therefore, necessary to adopt effective protocols for the diagnosis and prognosis of aging infrastructure, to ensure its performance over time along with properly planning for rehabilitation strategies, whether required. This work presents a two-stage case study of the S.I.T.E. building at the University of Ottawa for the diagnosis and prognosis of ASR-affected members (i.e., columns) after nearly 20 years in service. The diagnosis phase was conducted with the aim of evaluating the cause and extent of distress and interpreting its impact on the performance of the affected structure. First, a visual inspection was conducted to evaluate potentially damaged members, in order to select the best location for core-drilling. Once ASR was confirmed through petrographic examination, specimens were evaluated through the multi-level assessment (i.e., coupling of microscopic and mechanical assessment). A range of damage was discovered among the examined columns (i.e., 0.03%, 0.05%, and 0.08% expansion). Moreover, evidence of developing freeze and thaw (FT) damage was discovered in columns with greater levels of expansion, raising future concerns regarding the durability and serviceability of members affected by this coupling of damage (i.e., ASR+FT). For the second stage of this project (i.e., prognosis), a novel ASR semi-empirical model was developed with the aim of predicting future ASR-induced expansion and damage in the S.I.T.E. building. The above model was developed and validated (using ASR exposure site data) through the coupling of existing chemo-mechanical macro-models, which were used to predict material behaviour on the structural scale, and novel mathematical relationships for the prediction of anisotropy in the columns. Moreover, the use of the multi-level assessment to predict the mechanical implications of predicted distress was found to enhance the model’s capacity for prognosis and demonstrated important potential for the accurate prediction of multi-level damage in the S.I.T.E. columns.

Alkali activated materials (AAMs) represent construction materials with a huge potential especially because of environmental and economic aspects but sufficient mechanical properties as well. A fibre or fabric reinforcement of the AAMs could support more widespread application potential due to the mechanical properties, fracture toughness or composite durability improvement. Various alkaline activators were used for a blast furnace slag (BFS) activation to produce a suitable matrix for basalt fibres (BF) implementation in this thesis. The BFs represent applicable reinforcing material because of its favourable mechanical and thermal properties. Still, the utilization of BFs in the AAMs is quite limited due to the fibres low chemical stability under the alkaline conditions. Accelerated leaching tests with a determination of basalt fibres chemical composition same as tensile strength change using various analytical techniques (XRD, XPS, SEM-EDX, ICP-OES) have confirmed these assumptions. An influence of basalt fabric reinforcement in one or more layers on the mechanical properties was determined with the meaning of the compressive and flexural strengths. The fibre/matrix adhesion and transition zone properties were studied using SEM-EDX and pull-out tests as well because they are crucial parameters for the composite material reinforcement efficiency.

The diploma thesis is focused on the use of the waste glass with different fineness on alkali - activated composites, mainly based on slag and fly ash. The theoretical part is focused on materials that are most used for alkaline activation - slag, fly ash and their composites with waste glass. The theoretical part also deals with the alkaline activation of composites from these materials and the factors that influences the microstructure and properties of these composites. In the experimental part were prepared composites from slag and fly ash with a waste glass as substitute. These composites then have been examined on mechanical properties and microstructure, also how different fineness of glass influences these properties. Then it will be decided whether it is economically advantageous grinding waste glass to finer fractions

This thesis concerns on substitution of blast furnace slag or its part with fly ash in alkali-activated systems based on aluminosilikates. Classic, fluid bottom and fluid filter fly ashes will be tested. The goal is to prepare geopolymer with required mechanical properties, but with maximal admixture of alternative raw materials. In composites with substitutioned slag or its part the thesis focuses mainly on workabilityof fresh mixture, pressure and bending strenght. Use of secondary raw materials has advantages in the economic point of view and it´s friendly to enviroment, too.