O concreto armado é um dos materiais de construção mais utilizados atualmente. Um dos fatores que levaram a essa preferência foi a maior durabilidade dos componentes, uma vez que o aço inserido no concreto se protege do ambiente externo e, consequentemente, de uma agressividade intensa pelo cobrimento de concreto empregado. Porém, mesmo considerando que um concreto adequadamente dosado, lançado e curado tende a ser durável, casos de deterioração prematura das estruturas de concreto podem ocorrer, trazendo à tona a importância do controle dos fatores responsáveis pela degradação natural da estrutura. Entre os fatores de deterioração, destaca-se a corrosão de armaduras, devido a sua elevada incidência e potencial de dano. Nas estruturas de concreto armado, são utilizados espaçadores para garantir o cobrimento especificado em projeto e o consequente confinamento do aço, garantindo assim o aumento da vida útil da estrutura. No entanto, a interface espaçador-concreto pode se tornar um ponto frágil para a entrada de agentes agressivos, como os íons cloreto. O objetivo deste trabalho foi avaliar a influência dessa interface utilizando espaçadores de argamassa industrializados e espaçadores de plástico, bem como a condição de exposição a que o concreto é submetido. Para a viabilização do estudo, foi utilizada a técnica de aceleração de corrosão, baseada no ensaio denominado Corrosão Acelerada por Imersão Modificada (CAIM) com aplicação de voltagem constante e corrente constante. Foram moldados corpos de prova em laboratório, com dimensões de 10 × 10 × 20 cm, estabelecidas pelo CAIM, com a utilização de dois tipos de espaçadores e cobrimentos estabelecidos de 25 mm e 50 mm, além de uma barra de aço com diâmetro de 12,5 mm, simulando uma situação real. Para a avaliação dos dados, as amostras passaram por análise microscópica, ensaio colorimétrico e de redimensionamento a laser, a fim de realizar análises qualitativas e quantitativas dos resultados. Este estudo verificou que tanto espaçadores de argamassa quanto de plástico contribuíram para uma maior degradação na região dos espaçadores, porém os de plástico apresentaram desempenho inferior quanto à ascensão de cloretos já na fase da iniciação. Além disso, a condição de exposição por ciclos de calor influencia claramente na interface entre espaçador e concreto, em especial nos espaçadores de plástico. / Reinforced concrete is one of the building materials most used today. One of the factors leading to this constructive choice was greater durability, since the steel is protected for the concrete cover from a strong aggressiveness of the external environment. However, even considering that an adequately dosed, cast and cured concrete, tends to be durable, cases of premature deterioration of concrete structures can occur, bringing to the fore the importance of control the factors responsible for the natural degradation of the structure. Among the deterioration factors, can be highlighted the rebars’ corrosion, because of the high incidence and potential damage. In reinforced concrete structures, spacers are used to ensure structural design specified cover depths and the steel confinement, which helps to increase the structure service life. However, the spacer-concrete interface can become a weak point for the entry of aggressive agents, such as chloride ions. This study aims to understand the influence of the spacer-concrete interface, analysing industrialized mortar spacers and plastic spacers, as well the concrete subjected to different curing condition. In order to make this work possible, a corrosion acceleration technique was used, based on corrosion acceleration test method, with application of constant voltage and constant current. Samples sizing 100 x 100 x 200 mm were cast in the laboratory. The samples were subjected to accelerated corrosion process stimulation, using two different spacers and cover depths (25 mm and 50 mm) and one rebar diameter (12.5 mm), simulating a real situation. The losses of cross section were measured by using microscopic analysis, colorimetric tests and 3D image reconstruction with laser, in order to perform qualitative and quantitative analysis. The results show that both, mortar spacers as plastic spacers, contributed to increase the transport in the contact region, but the plastic spacers produced the largest increase at the first stages. Furthermore, the increase of the temperature in the condition of exposure analysis by heat cycles influences in the interface between spacer and concrete, particularly with the plastic spacers.

A busca pelo desenvolvimento sustentável impulsiona a pesquisa voltada ao uso de resíduos industriais na construção civil. Os resíduos da indústria de cerâmica vermelha podem ser utilizados como material pozolânico e já existem trabalhos que apontam para essa possibilidade. Porém, existe uma lacuna quanto à avaliação da durabilidade do concreto produzido com esse resíduo. Este trabalho analisa os efeitos da substituição de parte do cimento por resíduos de tijolos moídos (RTM) frente à corrosão da armadura provocada pela carbonatação e pela ação de cloretos. Para isso, foram preparados concretos convencionais (CCV) nos traços (aglomerante: materiais secos) 1:3,18; 1:4,11; e 1:5,58, cada um com 10%, 20% e 30% de RTM. Foram também analisados concretos autoadensáveis (CAA) com traço de 1:3 e 20%, 30% e 40% de substituição de resíduos, além dos traços sem resíduos usados como referências. O uso do RTM diminuiu o índice de vazios nos traços, porém houve perdas de resistência que alcançaram até 19% aos 90 dias. Os concretos autoadensáveis (CAA) mostraram melhores resultados de resistência apresentando melhoria em todos os traços para a mesma idade dos CCV, atingindo 11% de aumento. Em relação aos ensaios de carbonatação, os concretos com RTM tiveram maiores profundidades de carbonatação do que os concretos de referência, fato explicado pela redução da sua reserva alcalina. No entanto, esse aumento não inviabiliza o uso de concretos com RTM, principalmente para dosagens de menor porosidade e adições em patamares de substituição menos elevados Para a penetração de cloretos o RTM apresentou bom resultado, tanto para os CCV como para os CAA. Embora o RTM tenha diminuído o teor crítico de cloretos, ele aumentou o tempo necessário à despassivação das armaduras. Fato explicado pelo refinamento dos poros e pela maior capacidade de fixação de cloretos. Esse resultado é bastante animador para o uso deste resíduo em concretos convencionais expostos a ambientes marinhos ou como finos para concretos autoadensáveis. / The search for the sustainable development boosts the research focused on the use of industrial wastes civil construction. The industry wastes of red ceramics can be used as pozzolanic material and there are already works that point out for this possibility. However, there is a knowledge gap regarding the durability evaluation of the concrete produced with this waste. This research analyzes the effects substitution of part of the cement by crushed brick wastes (CBW) in relation to the reinforcement corrosion caused by carbonation and chloride action. For this reason, conventional cement concrete (CCV) was prepared in the traces (agglomerate: dry materials) 1:3,18; 1:4,11; and 1:5,58, each one with 10%, 20% and 30% of CBW. Self-compacting concrete (SCC) was also analyzed with trace of 1:3 and 20%, 30% and 40% of waste substitution, besides the traces with no waste used as references. The use of CBW decreased the rate of gaps in the traces, but there were losses of resistance that reached up to 19% in 90 days. The self-compacting concrete (SCC) showed better resistance results presenting improvement in all traces for the same age of the CCV, reaching 11% of increase. In regard to the carbonation tests, the CBW concretes had greater depths of carbonation than the reference concrete; fact explained by the reduction of its alkaline reserve. Nevertheless, this increase does not hamper the use of CBW concretes, especially for dosages of lower porosity and additions in lower substitution standards. For the chloride penetration, the CBW presented good result both for the CCV and the SCC. Although the CBW has diminished its critical chloride content, it increased the necessary period of time for reinforcement despassivation This fact was explained by the refining of pores and by the larger capacity of chlorides fixation. This result is very satisfactory for the use of this waste in conventional concretes exposed to marine environments or as fine aggregate for self-compacting concretes.

No presente trabalho, foi desenvolvida uma metodologia one-pot para obtenção de produtos 4-cloro-1-hidroxinaftaleno-2-oxazolinas (Cl-HNO) 4, utilizando um excesso de SOCl2 a partir da amida 3a. Para a formação do produto de interesse 4 foi desenvolvida uma proposta mecanística para a simultânea ciclização do anel 2- oxazolina e halogenção na porção do anel naftóico através de espectrometria de massas de alta resolução, difração de raios-x e cálculos teóricos. Em seguida, a hidrólise de 4 levou ao produto 5 com nova inversão de configuração no C4. Para funcionalização do ácido 5, foram reagidos grupos aminas e álcoois, conduzindo a uma pequena biblioteca de compostos inéditos com propriedades fluorescentes (6a-e, 7a-e) com Φf 0.8%-1.6%. Testes biológicos contra cepas de fungos foram realizadas. Em uma segunda etapa do trabalho, foi realizada a aplicação do anel 2-oxazolínico como ligantes em reações de acoplamento cruzado do tipo Suzuki-Miyaura. A síntese dos ligantes foi realizada em apenas dois passos reacionais, partindo das amidas 3a-c reagidas com Deoxo-Flúor® levando a três diferentes ligantes 8a-c. Os mesmos foram testados, e o ligante 8a levou aos produtos de acoplamento 9a-m com os melhores rendimentos de 59% a 95%. / In this work, we developed a new one-pot method for synthesizing 4-chlorinated 1- hydroxynaphthaleno-2-oxazoline (2-HNO) 4 by subjecting amide 3a to excess SOCl2. A mechanism for the formation of 4 is proposed, which involves simultaneous cyclization to form the 2-oxazoline ring and halogenation of the 2-hyrdoxynaphthalene ring. We present supporting evidence for this mechanism in the form of high resolution mass spectrometry, x-ray crystallography and theoretical calculations. Hydrolysis of 4 led to product 5 with inversion of configuration at C-4, confirmed by NMR spectra. To functionalize the acid 5, amines and alcohols were reacted with acid 5, leading to a small library of novel compounds having fluorescent properties (6a-e, 7a-e) with Φf 0.8%-1.6%. Furthermore, the library of compounds were used in biological testing against various strains of fungi. In the second stage of this work, we explored the application of the 2-oxazoline ring, through its use as a ligand in Suzuki-Miyaura cross-coupling reactions. The preparation of the ligands were obtained in only two reaction steps, starting from amides 3a-c were reacted with Deoxo-Fluor®, leading to three different ligands 8a-c, respectively. The same were tested, and the ligand 8a provided coupling products 9a-m in good yields of 59% to 95%.

Este trabalho apresenta o estudo da incorporação de fibra de vidro curta em composto rígido de poli(cloreto de vinila) - PVC - por meio de equipamentos e técnicas de processamento convencionais da indústria brasileira. Foram avaliadas as influências de: a) tamanho de fibra de vidro (tipo E), b) dosagem de fibra de vidro, c) dosagem de dióxido de titânio (TiO2) e d) a temperatura de processamento nas propriedades físicas, térmicas, mecânicas e na adesão entre matriz polimérica e fibra de vidro (analisada por Microscopia Eletrônica de Varredura). O custo-benefício dos compósitos foi calculado por meio de Índices de Mérito para os modos de carregamento mecânico encontrados nos tubos pressurizados para água fria (Cilindro com Pressão Interna) e perfis rígidos utilizados em construção civil (Barra em Flexão), dado o grande uso de PVC nestas aplicações. Entre os resultados obtidos, destaca-se o aumento de 45% no módulo de elasticidade para os compósitos com 20% de fibra de vidro moída que, para algumas aplicações, pode apresentar uma relação custo-benefício bastante favorável. / This work presents the impact of the short glass fiber incorporation in rigid PVC compound through conventional processing techniques currently employed in the Brazilian industry. It were studied the influences of a) glass fiber geometry (E type), b) glass fiber content, c) titanium dioxide content and d) processing temperature in the physical, mechanical and thermal properties. The adhesion conditions between polymeric matrix and glass fiber was analyzed by scanning electron microscopy (SEM). Cost-benefit relation of composites was evaluated using materials index technique for mechanical conditions found in pressurized water pipes (cylinder with internal pressure) and in building construction profiles (beam loaded in bending). The results attained suggested that, in some cases, the mechanical properties enhancement (such as the increase of 45% in the modulus of elasticity for composites containing 20% of glass fiber) and the processing techniques required to produce it can present an interesting cost-benefit relation.

This present study benchmarked the chloride resistance of concretes mixes at the limit state of BS 8500-1:2006 using the newly published CEN TS12390-11. Of the three allowed methodologies, the immersion test was carried out. At least two water-cement ratios were produced for each mix design to enable normalisation of the results. The performance of concrete was compared on the basis of equal compressive strength, i.e. 40 and 50 N/mm2 and an equal water-cement ratio of 0.45. In addition to the CEN TS 12390-11:2010, rapid test methods NT Build 492 and a steady-state migration test UNE 83987:2009 were also conducted. Selected concretes were also tested for cyclic wetting in artificial sea water and evolution of chloride diffusion over the test period. The ageing factor of concrete mixes, which describes the development of diffusion coefficient (D) from the unsteady to steady-state determined from this research was compared with those reported in The Concrete Society Technical Report 61. Test specimens for highway exposure were also produced for future research work. CEN has just agreed and published (at the time of the writing of this thesis) a test methodology for chloride resistance as a technical standard (CEN, 2010). The test method underpins the equivalent durability performance approach. Therefore, the use of this test was investigated in terms of evolution of the chloride diffusion, and effect of cyclic wetting and drying in artificial seawater exposure. As the test method is slow, (3 months to complete), other rapid test methods were also studied on the same specimens. The results from these tests were compared to look for the possibility of having a faster test methodology for chloride durability. Overall, the results showed that concrete mixes at the limiting value of BS 8500-1:2006 have a wide range of performance between 0.3 × 10-12 m2/s and 20 × 10-12 m2/s regardless of the test methods. Ranking of concrete according to performance shows that this changes with age. This is the same for all test methods although the rate of change is different between different test methods. However, the ranking of concrete at equal compressive strength and equal water-cement ratio follows the general order of (from best to worst) ggbs> fly ash> silica fume> limestone> CEM I. It was also postulated that there is a limit to the benefit of reducing water-cement ratio to improve durability. This is because of at very low water cement ratio, concrete may develop autogenous cracking that is detrimental to the porosity. Using the CEN TS 12390-11:2010 it was found that CEM I, fly ash and silica fume mixes follows the same ageing factor proposed by Concrete Society Technical Report 61 although ggbs shows a different ageing factor. The improvement of ggbs quality was attributed to this change. It was also found that 90 days test duration was optimum as a shorter period risks giving a non stable diffusion rate whilst longer than 90 days shows insignificant change in Dnss values. Exposure of selected concrete specimens to cyclic wetting and drying in artificial seawater elevated to 1 M NaCl equivalent shows reduced chloride diffusion. However, the mechanism controlling this is not clear. The thesis showed that some of the limiting value requirement for BS 8500-1:2006 does not meet the durability requirements for chloride resistance. There are some concrete mixes recommended that performs poorly in testing. The research reported also provides further understanding of the new CEN TS 12390-11:2010 in terms comparative ranking of cements up to the point of comparative performance between other tests methods. Validation of the ageing factor for chloride durability is also provided as well as the need for updates in the age factor values due to changes in the nature of cements.

Este trabalho apresenta o estudo da incorporação de fibra de vidro curta em composto rígido de poli(cloreto de vinila) - PVC - por meio de equipamentos e técnicas de processamento convencionais da indústria brasileira. Foram avaliadas as influências de: a) tamanho de fibra de vidro (tipo E), b) dosagem de fibra de vidro, c) dosagem de dióxido de titânio (TiO2) e d) a temperatura de processamento nas propriedades físicas, térmicas, mecânicas e na adesão entre matriz polimérica e fibra de vidro (analisada por Microscopia Eletrônica de Varredura). O custo-benefício dos compósitos foi calculado por meio de Índices de Mérito para os modos de carregamento mecânico encontrados nos tubos pressurizados para água fria (Cilindro com Pressão Interna) e perfis rígidos utilizados em construção civil (Barra em Flexão), dado o grande uso de PVC nestas aplicações. Entre os resultados obtidos, destaca-se o aumento de 45% no módulo de elasticidade para os compósitos com 20% de fibra de vidro moída que, para algumas aplicações, pode apresentar uma relação custo-benefício bastante favorável. / This work presents the impact of the short glass fiber incorporation in rigid PVC compound through conventional processing techniques currently employed in the Brazilian industry. It were studied the influences of a) glass fiber geometry (E type), b) glass fiber content, c) titanium dioxide content and d) processing temperature in the physical, mechanical and thermal properties. The adhesion conditions between polymeric matrix and glass fiber was analyzed by scanning electron microscopy (SEM). Cost-benefit relation of composites was evaluated using materials index technique for mechanical conditions found in pressurized water pipes (cylinder with internal pressure) and in building construction profiles (beam loaded in bending). The results attained suggested that, in some cases, the mechanical properties enhancement (such as the increase of 45% in the modulus of elasticity for composites containing 20% of glass fiber) and the processing techniques required to produce it can present an interesting cost-benefit relation.

The objectives of this research were 1) to investigate the effects of hydrodemolition treatment timing on chloride concentration profiles in concrete bridge decks for depths of concrete removal below the top mat of reinforcing steel and 2) to investigate factors that influence the occurrence of blow-throughs in concrete bridge decks when hydrodemolition is used. The research results are intended to provide engineers with guidance about the latest timing of hydrodemolition that can maintain a chloride concentration level below 2.0 lb of chloride per cubic yard of concrete at the levels of both the top and bottom mats of reinforcing steel, as well as about conditions that may indicate a higher probability of blow-through during hydrodemolition. The scope of this research included a questionnaire survey of hydrodemolition companies to summarize common practices in the field, numerical modeling of chloride concentration to investigate hydrodemolition treatment timing on typical Utah bridge decks, and structural analysis to investigate factors that influence the occurrence of blow-throughs during hydrodemolition. While some survey respondents indicated that certain parameters vary, the responses are valuable for understanding typical practices and were used to design the numerical experiments. The numerical modeling generated chloride concentration profiles through a 75-year service life given a specific original cover depth (OCD), treatment time, and surface treatment usage. The results indicate that, when a surface treatment is used, the concentration at either the top or bottom mat of reinforcing steel does not reach or exceed 2.0 lb of chloride per cubic yard of concrete after hydrodemolition during the 75 years of simulated bridge deck service life. The results also indicate that, when a surface treatment is not used, the chloride concentration at the top mat of reinforcement exceeds 2.0 lb of chloride per cubic yard of concrete within 10, 15, and 20 years for OCD values of 2.0, 2.5, and 3.0 in., respectively. The numerical experiments generated results in terms of the main effect of each input variable on the occurrence of blow-throughs and interactions among selected input variables. For each analysis, blow-through can be expected when the calculated factor of safety is less than 1.0. The factor of safety significantly increases with increasing values of transverse rebar spacing and concrete compressive strength and decreasing values of depth of removal below the bottom of the top reinforcing mat, orifice size, and water pressure within the ranges of these parameters investigated in this experimentation. The factor of safety is relatively insensitive to jet angle. For both case studies evaluated in this research, the blow-through analysis correctly predicted a high or low potential for blow-through on the given deck.

As the primary cause of concrete bridge deck deterioration in the United States is corrosion of the steel reinforcement as a result of the application of chloride-based deicing salts, chloride concentration testing is among the most common techniques for evaluating the condition of a concrete bridge deck. The objectives of this research were to 1) compare concrete drilling and powder collection techniques to develop a sampling protocol for accurately measuring chloride concentrations and 2) determine the number of chloride concentration test locations necessary for adequately characterizing the chloride concentration of a given bridge deck. Laboratory experiments on concrete drilling and powder collection were conducted to compare current concrete powder sampling techniques, including constant and stepwise drilling methods and spoon and vacuum powder collection methods. In addition, three charts were prepared to determine the number of chloride concentration test locations necessary for adequately characterizing the chloride concentration of a given bridge deck. The number of samples is dependent on reliability, spatial variability in chloride concentration, and an allowable difference between sample and population means. For the experiment on drilling, this research shows that the practice of decreasing the size of the drill bit in a stepwise fashion with increasing sampling depth reduces the possibility of abrading concrete from the sides of the hole above the sampling depth, where the chloride concentrations are higher, during drilling of lower lifts. For the experiment on powder collection, this research demonstrates that representative samples of concrete powder can be collected with either a spoon or a vacuum. Based on the results of this research, the stepwise drilling method and either the spoon or vacuum powder collection method are recommended for application. In addition, the charts developed in this research are recommended for estimating the number of chloride concentration test locations necessary for adequately characterizing the chloride concentration of a given bridge deck. This research will be helpful in effectively assessing the condition of concrete bridge decks with respect to chloride-induced corrosion of the reinforcing steel and prioritizing bridge maintenance and rehabilitation projects.

abstract: Mineral weathering and industrial activities cause elevated concentration of hexavalent chromium (Cr(VI)) in groundwater, and this poses potential health concern (>10 ppb) to southwestern USA. The conversion of Cr(VI) to Cr(III) – a fairly soluble and non-toxic form at typical pH of groundwater is an effective method to control the mobility and carcinogenic effects of Cr(VI). In-situ chemical reduction using SnCl2 was investigated to initiate this redox process using jar testing with buffered ultrapure water and native Arizona groundwater spiked with varying Cr(VI) concentrations. Cr(VI) transformation by SnCl2 is super rapid (<60 seconds) and depends upon the molar dosage of Sn(II) to Cr(VI). Cr(VI) removal improved significantly at higher pH while was independent on Cr(VI) initial concentration and dissolved oxygen (DO) level. Co-existing oxyanions (As and W) competed with Cr(VI) for SnCl2 oxidation and adsorption sites of formed precipitates, thus resulted in lower Cr(VI) removal in the challenge water. SnCl2 reagent grade and commercial grade behaved similarly when freshly prepared, but the reducing strength of the commercial product decreased by 50% over a week after exposing to atmosphere. Equilibrium modeling with Visual MINTEQ suggested redox potential < 400 mV to reach Cr(VI) treatment goal of 10 ppb. Kinetics of Cr(VI) reduction was simulated via the rate expression: r=-k[H+]-0.25[Sn2+]0.5[Cr2O72-]3 with k = 0.146 uM-2.25s-1, which correlated consistently with experimental data under different pH and SnCl2 doses. These results proved SnCl2 reductive treatment is a simple and highly effective method to treat Cr(VI) in groundwater. / Dissertation/Thesis / Masters Thesis Civil, Environmental and Sustainable Engineering 2019

Les objectifs de ma thèse ont été de caractériser le développement du gradient en ions chlorures dans les cellules de Purkinje dans un modèle d'étude de l'autisme : les souris exposées de façon prénatale au valproate de sodium. A cette fin, j'ai effectué des mesures éléctrophysiologiques de courants GABAergiques au cours du développement post-natal de ces animaux et des observations histologiques de la densité linéaire en cellules de Purkinje. D'autre part, j'ai participé à une étude comportementale visant à étudier l'influence d'un composé modulant le gradient en ions chlorures dans deux modèles génétiques d'étude de l'autisme : les souris Oprm1-/- et les souris Fmr1-/-. Au cours de ma thèse, j'ai mis en évidence un retard du développement du gradient en ions chlorures. J'ai également montré qu'une exposition prénatale au valproate de sodium induisait une perte post-natale en cellules de Purkinje. Enfin, le composé avec lequel j'ai travaillé améliore le phénotype autistique et laisse entrevoir un fort potentiel translationnel. / The aims of my PhD were to characterize the development of the chloride gradient in Purkinje cells in a model of autism: mice prenatally exposed to sodium valproate. To this end, I measured GABAergic currents along the post-natal development of these mice and made histological observations of the Purkinje cells linear density. Secondly, I took part of a behavioral study to test the influence of a compound acting on the chloride gradient in two genetic models of autism: Oprm1-/- and Fmr1-/- mice. During my thesis I showed a delay in the development of the chloride gradient. I also observed that a prenatal exposition of sodium valproate induced a post-natal Purkinje cells loss. Finally, the compound I worked with improves the autistic phenotype and opens the perspective for translational potential.