A racionalização e industrialização da construção promoveram profundas modificações no processo construtivo e nas técnicas gerenciais no Brasil. Muitas empresas construtoras, para garantir competitividade no mercado, buscaram soluções capazes de aumentar a velocidade de suas obras, tais como a redução do período de escoramento. A retirada antecipada do escoramento submete a estrutura a carregamento precoce, podendo desencadear a microfissuração do concreto. Como consequência, as deformações instantâneas e lentas tendem a aumentar e, consequentemente, manifestações patológicas podem ocorrer com maior intensidade. Objetivando simular o dano causado pela retirada antecipada do escoramento em idades iniciais, este trabalho investigou a influência do carregamento precoce por compressão axial na durabilidade de concretos distintos. O programa experimental foi executado em duas etapas. A primeira, investigou a influência da microfissuração causada por carregamento precoce na durabilidade de concretos produzidos com três tipos de cimento (CPV-ARI, CPIV RS e CPII Z) e três relações água/cimento (0,35, 0,50 e 0,70). Os carregamentos dos corpos de prova foram realizados em laboratório nas idades de 1, 3 e 7 dias. Para cada idade de carregamento foram rompidas, até o limite, duas amostras de referência e, a partir do valor médio de ruptura obtido, determinava-se os percentuais de carga (25%, 50% e 75%) que seriam aplicados nos concretos. Após o período de cura de 28 dias, as amostras foram ensaiadas à Penetração de Íons Cloreto e à Absorção Capilar de Água. A segunda etapa do programa experimental investigou a influência do prolongamento da cura na recuperação do dano causado pelo carregamento dos concretos nas primeiras idades. Foram produzidos concretos com dois tipos de cimento (CPV-ARI e CPIV) e uma relação água/cimento (0,50). Parte dos concretos receberam pré-carregamento de 75% da carga de ruptura na idade de 3 dias e parte permaneceu intacta, para servir como referência. Os ensaios mecânicos e de durabilidade (penetração de íons cloreto) foram executados ao longo do tempo (3, 7, 28 e 91 dias). Os resultados da Etapa 1 mostraram que, para todas as misturas investigadas, houve elevação da penetração de cloretos e da absorção de água com o aumento da intensidade do carregamento e da relação água/cimento dos concretos. Também foi observado a existência de um processo de microfissuração causado pela ação dos pré-carregamentos dos concretos com pouca idade. Os melhores desempenhos foram obtidos para as misturas com cimentos pozolânicos e não submetidas ao carregamento. Os resultados observados na Etapa 2 mostraram que o aumento do período de cura dos concretos refletiu positivamente nos resultados dos ensaios mecânicos e de durabilidade. Nessa etapa, também foram realizados ensaios microestruturais complementares que permitiram observar que a continuidade da cura promoveu uma recuperação parcial das microfissuras (self-healing) nos concretos. No entanto, nem todas foram fechadas. Constatou-se que as magnitudes das microfissuras remanescentes eram tal que poderiam se tornar um caminho preferencial para a entrada de íons cloreto nos concretos. Conclui-se que todos os concretos analisados apresentaram a mesma tendência de comportamento, de redução da entrada de íons cloreto com o aumento do período de cura. No entanto, o diferencial dos resultados foi notado na intensidade dos valores observados, significantemente reduzidos para os cimentos pozolânicos. / The rationalization and industrialization of the construction promoted deep changes in the constructive process and on the management techniques in Brazil. Most of the construction companies look for solutions that allow it to increase the speed of the constructions to ensure competitiveness on the market, such as the reduction on the time of structure execution, as well as the period of scores and anticipating the beginning of the masonry building. The early removal of the scores put the structure in an early loading without giving enough time to part of the cement hydration reactions happen, starting the concrete micro cracking process. Consequently, the instantaneous and slow deformations tend to increase and hence, pathologies may occur with greater intensity. This work researches the influence of early loading, by axial compression, in the durability of different types of concrete. The experimental program was implemented in two stages. The first stage investigated the influence of the micro cracking caused by pre loading on the durability of concretes produced with three different types of cement classified based on the Brazilian standards (CPV-ARI, CPIV RS and CPII Z) and three water/cement ratios (0.35, 0.50 and 0.70). The samples loading were realized in laboratory at the ages of 1, 3 and 7 days. Two reference samples were loaded until the limit, for each age of loading, and according to this average value of loading the percentage of loading to be applied on the samples in order to perform the durability tests were calculated (25%, 50% and 75%). The samples were placed in humid chamber for 28 days. After the cure period the samples were tested to Chloride ions penetration and water capillary absorption. The second stage of the experimental program investigated the influence of prolonged healing in the recovery of the damage caused by the concrete loading at early ages (microcracks). Concretes were produced with two types of cement (CPV-ARI and CPIV) and a water/cement ratio of 0,50. Part of the concrete received preload 75% of the tensile strength at age 3 days and some remained intact to serve as reference. The mechanical and durability tests were performed over time (3, 7, 28 and 91 days). The results of the first stage of the experimental program demonstrated that, for all the cements the increasing of the chloride penetration and water absorption is directly related with the increasing of the pre loading applied, to the increasing of the water/cement ratio on the mixture and the reduction of the age of the pre loading.The results obtained in Stage-1 confirmed the existence of a microcracking process caused by the action of the preload concrete at a young age. The best performances were observed for mixtures with pozzolan cement and not subjected to loading. The continued healing promoted a partial recovery of microcracks, verified by scanning electron microscopy images (SEM). However, not all were closed. It was found that the magnitude of the remaining microcracks were such that it could become a preferred path for the entry of chloride ions in concrete. All examined concrete showed the same trend behavior, reduction of the entrance of chloride ions with increasing curing period. However, the spread of results was noticed in the intensity of the observed values, significantly reduced for pozzolanic cements.

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2015-03-27T11:14:41Z No. of bitstreams: 2 Dissertação - Leonardo Gomes de Sá e Carvalho - 2014.pdf: 5044636 bytes, checksum: 3871b0d2777c9ab38b3d7c7cb34138cc (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-03-27T14:38:00Z (GMT) No. of bitstreams: 2 Dissertação - Leonardo Gomes de Sá e Carvalho - 2014.pdf: 5044636 bytes, checksum: 3871b0d2777c9ab38b3d7c7cb34138cc (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-03-27T14:38:52Z (GMT). No. of bitstreams: 2 Dissertação - Leonardo Gomes de Sá e Carvalho - 2014.pdf: 5044636 bytes, checksum: 3871b0d2777c9ab38b3d7c7cb34138cc (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-01-24 / Corrosion of reinforcement in concrete structures constitutes one of the most serious and costly problems to be solved in construction. Currently, a number of professionals are somehow mobilized in order to prevent, control and repair concrete structures subjected or with steel corrosion. This paper presents and discusses the main results of an experimental study aimed to verify the corrosion resistance of two different types of steel, CA24 and CA50. The CA24 steel was widely used in construction of the 1930s to 1960s, and CA50 steel is the most currently employed as reinforcement of concrete structures. Besides the type of steel, the study evaluated the influence of bar diameter (5mm and 25mm ) in the process of passivation, depassivation and propagation of corrosion. For the study, steel bars 5mm and 25mm, of the CA24 and CA50 were introduced in body-of-proof molded prismatic with a reference concrete. The bodies of the specimen underwent regular cycles of immersion in NaCl solution with 2 % concentration and drying. Were also shaped bodies-specimens with 3% sodium chloride in the mixing water by mass of cement. These remained initially in place with controlled humidity 55 ± 15 % and subsequently passed through cycles of immersion in clean water and drying. Monitoring for 210 days, the corrosion was evaluated by the electrochemical corrosion potential measurements (Ecorr) and polarization resistance (icorr). The concrete was monitored by measurements of surface resistivity (ρ). Before corrosion valuation, metallographic tests, chemical composition and mechanical tests for steel characterization were performed. The electrochemical mass loss were compared with the gravimetric weight loss, showing that steel CA50 to CA24 in comparison, is more susceptible to corrosion. The study also showed that steels with smaller diameter have lower corrosion resistance. / A corrosão de armaduras em estruturas de concreto constitui-se em um dos problemas mais sérios e onerosos a serem resolvidos na construção civil. Atualmente, vários profissionais estão mobilizados no sentido de prevenir, controlar e reparar estruturas sujeitas ou com corrosão de armaduras. O presente trabalho apresenta e discute os principais resultados de uma pesquisa experimental cujo objetivo foi verificar a resistência à corrosão de dois diferentes tipos de aço, o CA24 e o CA50. O aço CA24 foi amplamente empregado nas construções das décadas de 40 a 60, e o aço CA50 é o mais empregado atualmente como armadura de estruturas de concreto. Além do tipo de aço, o estudo avaliou a influência do diâmetro da barra (5mm e 25mm) nos processos de passivação, despassivação e propagação da corrosão. Para a realização do estudo, foram introduzidas barras de aço de 5mm e 25mm, de CA24 e CA50, em corpos-de-prova prismáticos moldados com um concreto de referência. Os corpos-de-prova foram submetidos a ciclos regulares de imersão, em solução de 2% de NaCl com 2%, e secagem. Foram moldados, também, corpos-de-prova com 3% de cloretos de sódio na água de amassamento, em relação à massa de cimento. Estes permaneceram, inicialmente, em local com umidade controlada de 55 ± 15% e, posteriormente, passaram por ciclos de imersão em água potável e secagem. Durante 210 dias de monitoramento, a corrosão foi avaliada por meio das medidas eletroquímicas de potencial de corrosão (Ecorr) e resistência de polarização (icorr). O concreto foi monitorado por meio de medidas de resistividade superficial (ρ). Antes do inicio dos ensaios de corrosão, foram realizados os ensaios de metalografia, composição química e ensaios mecânicos, para a caracterização das barras de aço. As perdas de massa eletroquímicas foram comparadas com as perdas de massa gravimétricas, mostrando que o aço CA50, em comparação ao CA24, é mais suscetível à corrosão. O estudo mostrou também que aços com menor diâmetro possuem menor resistência à corrosão.

Neste trabalho foi estudada a degradação eletroquímica do azo corante Preto Ácido 210 (PA210) utilizando ânodos dimensionalmente estáveis de composição Ti/Ir0,10Sn0,90O2 e Ti/Ir0,30Sn0,70O2 preparados pelo método de decomposição térmica de precursores poliméricos. Os efeitos da presença e da concentração de cloreto, da composição eletródica, da densidade de corrente e do tempo de eletrólise sobre a oxidação eletroquímica de 100 ppm do corante PA210 foram avaliados. Em todas as condições estudadas, a remoção da absorbância em 465 nm (max) foi superior a 94% depois de 30 min de eletrólise. A redução de TOC foi proporcional à concentração de íons cloreto no eletrólito e não mostrou dependência da composição eletródica. A formação de espécies organocloradas variou na faixa de 8 a 16 ppm, sendo que as maiores concentrações de AOX foram obtidas para o eletrólito com maior concentração de cloreto. A redução máxima de TOC obtida foi de 25% depois de 90 min de eletrólise à densidade de corrente de 25 mA cm-2 para o eletrólito HCl 0,1 mol L-1. A eficiência de corrente foi calculada em relação ao TOC, sendo obtido o melhor resultado, de 9,14%, em 30 min de eletrólise com HCl 0,1 mol L-1 a 25 mA cm-2, sendo esta eficiência quatro vezes maior que para melhor eficiência em meio de H2SO4 0,1 mol L-1. O estudo da relação TOC / AOX indica que após as eletrólises houve a adição de cloreto as substâncias orgânicas gerando espécies organocloradas que apresentam uma relação de aproximadamente 1 átomo de cloro para cada 5 átomos de carbono. / The electrochemical degradation of the azo dye Acid Black 210 (AB210) using dimensionally stable anodes of composition Ti/Ir0,10Sn0,90O2 and Ti/Ir0,30Sn0,70O2 prepared by thermal decomposition of polymeric precursors was studied. The effects of the presence and concentration of chloride, electrode composition, current density, and electrolysis time on the electrochemical oxidation of 100 ppm dye PA210 were evaluated. In all the studied conditions, the removal of the absorbance at 465 nm (max) was greater than 94% after 30 min of electrolysis. The reduction of TOC was proportional to the concentration of chloride ions in the electrolyte and was not shown to be dependent on electrode composition. The formation of organochloride species varied in the range from 8 to 16 ppm, with higher concentrations of AOX being obtained for the electrolyte with high chloride concentration. The maximum reduction of TOC was 25% after 90 min of electrolysis, at a current density of 25 mA cm-2, for the electrolyte HCl 0.1 mol L-1. The current efficiency was calculated in relation to TOC, and the best result was 9.14% after 30 min of electrolysis in HCl 0.1 mol L-1 at 25 mA cm-2. This efficiency is four times higher than the best efficiency obtained by using only H2SO4 0.1 mol L-1 as electrolyte. The study of the TOC / AOX relationship indicates that there was addition of chloride to the organic substances after electrolysis, thus genetaring organochloride species with a ratio of about 1 atom of chlorine for every 5 carbon atoms.

O presente trabalho avalia o método de extração eletroquímica de íons cloreto na reabilitação de estruturas de concreto com problemas de corrosão de armaduras. Essa metodologia pode ser utilizada para evitar as desvantagens da recuperação tradicional do reparo localizado. No procedimento experimental foram realizados ensaios de laboratório em corpos-de-prova de forma prismática com dimensões reduzidas, moldados com diferentes relações água/cimento. A penetração de cloretos nos corpos-de-prova foi realizada de maneiras distintas: câmara de névoa salina e semiciclos de secagem e imersão parcial. Entre outros aspectos, foi avaliada a influência da espessura de cobrimento e da relação água/cimento na resposta do método através da determinação do teor inicial e final dos íons cloreto.Nas conclusões observa-se que a eficiência desse método foi até superior à encontrada em outros trabalhos da literatura. Nas séries cuja penetração de cloretos se deu através da câmara de névoa salina em média foram removidos 78% dos íons cloreto inicialmente presentes no concreto, nas séries onde a penetração de cloretos foi por semiciclos de secagem e imersão parcial obteve-se 91% de eficiência de remoção. / This present project evaluates the method of electrochemical extraction of chloride ions for the rehabilitation of concrete structures with reinforcement corrosion problems. This methodology can be used to prevent the disadvantages of traditional repair strategies in the patch repair. In the experimental procedure, tests performed in laboratory with specimens of prismatic form with reduced dimensions had been carried through, molded with different water/cement ratio. The chloride penetration in the specimens was carried through in distinct ways: salt spray chamber and semi cycles of drying and partial immersion. Among others aspects, the influence of the concrete cover and the water/cement ratio has been evaluated in the efficiency of method by determining the initial and the final chloride content. In the conclusions it is noticed that not only the test results did verify that this method successfully extracted chloride ions but it was much more efficient than previously reported in the literature. In the series where chloride penetration comes through the salt spray chamber, on average, this method removed 78% of the content of initial chloride ions in the concrete, in the series where the chloride penetration was done by semi cycles of drying and partial immersion, 91% of removal efficiency was obtained.

No description available.

Made available in DSpace on 2014-12-17T14:06:49Z (GMT). No. of bitstreams: 1 MauricioRP.pdf: 769557 bytes, checksum: 64ad674a4bbb41883e038d57b445215c (MD5) Previous issue date: 2008-11-10 / Lightweight concrete has been the subject of several studies towards the development of new building materials. Emphasis has been given on the particle size effect and nature of aggregates used as raw materials. The present study includes an analysis of the materials that make this kind of concrete, analyzes of mechanical properties such as compressive and tensile strength, in addition to assessments of the interface concrete aggregate/matrix interface, porosity and absorption profile of chloride ions in lightweight concrete based on expanded clay. The experiments were carried out by molding cylindrical samples 100 mm in diameter and 200 mm in height. The dosage experiments were performed without additives or with the addition of minerals: (T1) 1: 2.01: 1.10: 0.78 (T2) 1: 2.00: 1.32 : 0.62 - (T3) 1 :1.93 :1.54: 0.47 (cement : sand : expanded clay 0500 : expanded clay 1506).The water to cement ratio was set to 0.43. Expanded clay minerals with different average particle sizes were used, i.e., 9.5 mm/0500 and 19 mm/1506. The larger aggregate was coated by a glassy layer, yielding lower water absorption characteristics to the concrete. The results showed that the use of light expanded clay aggregates is a technically interesting solution to the production of lightweight concrete for construction applications / Considerando-se as tend?ncias de novos materiais na Constru??o Civil, o concreto leve tem sido objeto de v?rios trabalhos, com ?nfase na granulometria e suas mat?rias primas. Incluem-se neste estudo a altera??o de tra?os e dos materiais que comp?em esse concreto, analisando altera??es nas propriedades mec?nicas como resist?ncia ? compress?o e tra??o por compress?o diametral, al?m da interface agregado/matriz, porosidade e perfil de absor??o de ?ons cloreto no concreto leve ? base de argila expandida. Os experimentos foram realizados atrav?s de moldagem de corpos de prova cil?ndricos, com 100 mm de di?metro e 200 mm de altura. A dosagem experimental foi efetuada sem aditivos ou adi??es minerais, nos tra?os unit?rios em massa: (T1) 1 : 2,01 : 1,10 : 0,78 (T2) 1 : 2,00 : 1,32 : 0,62 - (T3) 1 : 1,93 : 1,54 : 0,47 (cimento : areia : argila expandida 0500 : argila expandida 1506); fixando-se a rela??o ?gua/cimento em 0,43. Para tanto, utilizou-se como agregado gra?do uma argila expandida, nas gradua??es 9,5 mm/0500 e 19 mm/1506. A argila de gradua??o maior era revestida com uma camada vitrificada, o que propiciou menor absor??o de ?gua pelo concreto. Os resultados mostraram que a utiliza??o da argila expandida como agregado leve ? uma solu??o tecnicamente vi?vel na produ??o de concreto leve para Constru??o Civil.

Class of 2012 Abstract / Specific Aims: The epithelial sodium channels (ENaC) found on the apical membranes of epithelial cells including those lining the respiratory tract are the rate limiting step of the absorption of excess fluid from the airspace of the alveoli. ENaC function is modulated by the effects of various physiologic signals such as the adrenergic and purinergic pathways, in addition to other local channels which control the flow of negatively charged ions such as the cystic fibrosis transmembrane conductance regulator (CFTR). We sought to determine the influence of genetic variation on the alpha subunit of ENaC at amino acid position 663 on baseline exhaled ions and pulmonary function in patients with CF. Methods: We assessed pulmonary function ( forced vital capacity[FVC], forced expiratory volume in one second [FEV1], forced expiratory flow maximum[FEFmax]) using a Medical Graphics cardiopulmonary testing device (Minneapolis, MN). Measures of exhaled sodium (Na+) and chloride (Cl-) were obtained using exhaled breathe condensate collected on a Jaeger Ecoscreen condenser unit (Cardinal Health, Yorba Linda, CA) with Na+ quantification using an atomic absorption spectrophotometer (Analyst 100; Perkin Elmer, Norwalk, CT) and Cl- anion quantification using a Dionex AS11 HC column. Healthy n=31 (n=18[58%], 9[29%], and 4[13%] subjects; Body mass index (BMI)=23±1, 25±2, and 25±2kg/ m2 for AA, AT and TT groups respectively). CF n= 42 (n=33[79%], 7[16%], and 2[5%] subjects; BMI equals 23±7, 19±0.4, and 20±2.2kg/m2 for AA, AT and TT groups respectively). Main Results: We found that the distribution of genotypes in CF differed from healthy subjects, with the AA genotype in 80% of CF and 59% in healthy. No significant difference were demonstrated in healthy subjects between genotype groups for pulmonary function and exhaled chloride while the genotypes did differ in exhaled Na (Na=2.9±0.4, 1.7±0.3, and 3.7±1.1mmol/L for AA, AT, and TT respectively, ANOVA p=0.07). CF subjects with the AA genotype had a higher baseline exhaled Cl-, FEV1, and FEFmax than those in the AA group (Cl=0.125±0.038,0.0 27±0.007, and 0.033±0.02 mmol/L ; FEV1=71±5, 68±11, and 40±22L; FEFmax=86±4, 72±7, and 44±24L/sec; for AA, AT, and TT respectively, ANOVA p<0.05, Tukey [AA vs. TT] p<0.05) while exhaled Na+ and FVC were similar between genotypes. Conclusions: Our results suggest that CF subjects with the AA genotype of the alpha subunit of the ENaC have a higher baseline exhaled Cl- and a resulting increase in pulmonary function when compared to the overactive TT groupCF patients with the TT αENaC genotype are likely candidates for early identification and treatment with inhaled ENaC inhibitors or other modulators of this pathway in order to improve survival.

La corrosion des armatures est reconnue comme la première cause de dégradation des structures en béton armé dans les domaines du génie civil et des monuments historiques. La corrosion peut survenir lorsque le béton d'enrobage est carbonaté ou lorsque les ions chlorure sont présents en quantité suffisante au niveau de l'armature.Les objectifs de cette thèse visent à appréhender les processus de corrosion des armatures lorsque le béton est doublement contaminé (carbonatation et ions chlorure) et d'évaluer une solution de réparation de type traitement électrochimique d’extraction des ions chlorure (ECE).Pour répondre à ces objectifs, trois phases ont été programmées : (1) des vieillissements artificiels, (2) un traitement ECE et (3) un suivi de la durabilité du traitement. Pour chacune de ces phases, les évolutions (1) de la corrosion des armatures dans le béton, (2) des produits de corrosion à l'interface armature/béton et (3) de la matrice cimentaire ont été investiguées. L'approche scientifique de l'étude, avec des analyses multiples d'observations à différentes échelles et l'utilisation de techniques non destructives, destructives ou in situ, a permis de rendre compte des processus de corrosion avant et après traitement et de discuter les résultats en fonction de critères d'efficacité proposés.L'étude a été réalisée en prenant en compte deux ciments (CEM I et CEM III/A) et en considérant deux modes de vieillissements artificiels. Trois cent vingt éprouvettes en micro-béton armé répondant à quatre formulations ont ainsi été étudiées. Les techniques principales utilisées sont des caractérisations électrochimiques non destructives, des caractérisations au MEB et EDS, des analyses destructives de déterminations quantitative pour la teneur en ions chlorure et qualitative pour l'évaluation du pH et enfin la microspectrométrie Raman qui permet de déterminer la nature des produits de corrosion in situ.L’exploitation de l’ensemble des résultats a mis en évidence l’évolution des caractéristiques étudiées au cours des phases de l’étude. Avant traitement, l'enrobage béton était entièrement carbonaté et la teneur en ions chlorure libres au voisinage de l'armature était comprise entre 0,9 et 2,1% par rapport à la masse de ciment en fonction des formulations. Les courants de corrosion étaient de l’ordre de 10 µA/cm² et une épaisseur de corrosion homogène de l’ordre de 5-10 µm était observée. Lors des analyses Raman in situ, de la rouille verte chlorurée a été identifiée, synonyme de corrosion active. Après traitement, plus de 90% des ions chlorure ont été extraits et le pH du béton au voisinage de l'armature a augmenté (pH>9) sur une épaisseur d’environ 1 cm. Les courants de corrosion sont devenus inférieurs à 0,1 µA/cm² (niveau de corrosion négligeable). La formation de magnétite a majoritairement été observée avec néanmoins la présence résiduelle très locale de rouille verte. Aucune évolution délétère significative de la matrice cimentaire n’a été identifiée. L’efficacité du traitement a donc été démontrée. L'évaluation de la durabilité du traitement sur une période de 4 à 12 mois a montré que les caractéristiques électrochimiques restaient stables. En revanche, la diminution de l'épaisseur de béton dont le pH avait augmenté pour les éprouvettes fabriquées avec le ciment CEM III/A peut laisser craindre une reprise de corrosion sur du plus long terme. Enfin, le suivi Raman in situ, montre des différences de la durabilité en fonction de la durée du traitement / Reinforcement corrosion is known as the first cause of reinforced concrete degradation in the fields of civil engineering structures and historical monuments. Corrosion occurs when concrete cover is carbonated or when chloride ions are present in sufficient quantity at the reinforcement vicinity.The main objectives of this thesis are to investigate the corrosion processes of the reinforcement when the concrete is contaminated by carbonation as well as chloride ions and to evaluate a cathodic electrochemical treatment as a repair solution.To meet these objectives, three phases were investigated: (1) artificial agings, (2) an electrochemical chloride extraction (ECE) treatment and (3) durability. For each of these phases, the evolutions (1) of the rebar corrosion in concrete, (2) of the corrosion products at the reinforcement/concrete interface and (3) of the cementitious matrix were studied.The scientific approach gathered multiple analyzes at different scales and the use of non-destructive, destructive or in situ technique. It allowed to study the corrosion processes before and after treatment and to discuss results according to efficiency criteria suggested.The study was carried out taking into account two cements (CEM I and CEM III/A) and considering two modes of artificial aging. More than three hundred specimens of reinforced micro-concrete, corresponding to four concrete designs, were therefore studied. The main techniques used were non-destructive electrochemical characterizations, SEM and EDS characterizations, destructive quantitative determinations (chloride ion content) and qualitative determinations (pH evaluation), and finally Raman microspectrometry to determine the nature of the corrosion products.The results highlighted some evolutions of different characteristics studied during the phases of the study. Before treatment, the concrete cover was entirely carbonated and the free chloride content at the reinforcement level was in the range of 0.9-2.1% by weight of cement depending on the concrete design. A 10 μA/cm² average corrosion currents was reported and a homogeneous corrosion layer thickness of about 5-10 μm was observed. During in situ Raman analysis, chloride green rust was identified indicating an active corrosion.After treatment, more than 90% of the chloride ions were extracted and the thickness of the concrete which had a pH value higher than 9 around the reinforcement, was about 1 cm. The corrosion currents became less than 0.1 μA/cm² (negligible corrosion level). The formation of magnetite was mostly observed with nevertheless a local presence of residual green rust. No significant deleterious evolution of the cementitious matrix was identified. The treatment efficiency was therefore demonstrated. The evaluation of the treatment durability over a period of 4 to 12 months showed that the electrochemical characteristics remained stable. On the other hand, a decrease in the concrete area which pH increased during the electrochemical treatment was observed for CEM III/A cement which could lead to a corrosion recovery over the longer term. Finally, the in situ Raman study revealed differences in durability as a function of the treatment duration

A influência de pequenas concentrações de íons cloreto na cinética de redução eletroquímica dos íons Bi3+ e Cu2+ foi estudada através de medidas independentes de adsorção específica e de cinética eletroquímica. A adsorção específica foi determinada por meio das curvas eletrocapilares obtidas com o método do tempo de gota, para soluções aquosas de misturas de ácido clorídrico xM e de ácido perclórico (1 - x)M. Obeservou-se que, em concentrações de cloreto muito baixas, iguais ou inferiores a 10-2 M, a adsorção específica desses íons segue a isoterma de adsorção de Henry. A cinética da redução eletroquímica dos íons de Bi3+ e Cu2+, na presença de pequenas concentrações de íons cloreto, em meio de ácido perclórico 1 M, foi estudada por polarografia com o eletrodo de mercúrio. Os valores das constantes de velocidade foram calculados, a partir da relação existente entre a corrente, medida em cada potencial, e a corrente de difusão, usando as equações relativas a processos de eletrodos irreversíveis. Estes valores mostraram que, para as concentrações mais baixas de cloreto estudadas, esses íons aceleram as reações Bi3+ + 3e &#8594; Bi(Hg) e Cu2+ + 2e &#8594; Cu(Hg). O mecanismo de redução, por outro lado, permanece o mesmo já observado por outros autores em soluções de ácido perclórico puro, ou seja, os íons Bi3+ e Cu2+ são reduzidos em etapas de um elétron com velocidades comparáveis. No caso do bismuto, para as concentrações mais altas de cloreto estudadas, o efeito da complexação dos íons Cl- e Bi3+ no meio da solução se torna apreciável e a influência dos íons cloreto na velocidade de redução se deve a uma ação combinada da sua adsorção específica sobre o eletrodo e da sua tendência em formar complexos. No caso do cobre apenas a adsorção específica dos íons cloreto é a responsável pelo seu efeito na cinética do processo, em virtude da não complexação dos íons Cl- e Cu2+ presentes na solução. Tanto no caso do bismuto como o do cobre se observou uma relação linear entre os logaritmos das constantes de velocidade de redução e a carga especificamente adsorvida de íons cloreto, a um potencial constante. Esses resultados estão em concordância com os modelos teóricos de PARSONS e de GUIDELLI e FORESTI, sobre a influência de íons não eletroativos especificamente adsorvidos na cinética de reações de eletrodo. presença de uma carga especificamente adsorvida, dependente do potencial do eletrodo, justifica a variação no coeficiente de transferência à medida que se varia a concentração do íon especificamente adsorvido; no caso do cobre, onde apenas a adsorção específica é a responsável pelo aumento da velocidade de redução eletroquímica, a correção no valor do coeficiente de transferência a partir dos dados de adsorção, coincide com os resultados experimentais obtidos a partir da variação do logaritmo da constante de velocidade com o potencial. / In the present work, the effect of chloride ions in small concentrations on the electrochemical reduction of Bi3+ and Cu2+ ions was studied by means of independent measurements of specific adsorption and electrode kinetics. Specific adsorption was calculated irom electrocapillary curve data, obtained by means of the drop time method for aqueous solutions of xM hydrochloric acid and (1 - x)M perchloric acid mixtures. It was observed that, for low chloride concentrations (less than or equal to 10-2M), specific adsorption of these ions on the mercury electrode obeys the Henrys adsorption isotherm. The kinetics of the electrochemical reduction of Bi3+ and Cu2+ ions, in the presence of emall concentrations of chloride ions in 1M HC104 was studied by dropping mercury electrode polarography. The rate constants was calculated from the ratio between the current, measured at each potential, and the diffusion current, using the equations for irreversible electrode processes. It is shown from these rate constansts, that for the smaller chloride concentrations, the velocity of the reaction Bi3+ + 3e &#8594; Bi(Hg) and Cu2+ + 2e Cu(Hg) is increased by the presence of chloride ions. The reduction mechanism remains the same as that observed by other investigators in pure HC104, i.e., the reduction occur in one electron steps and the rates of each step are compa¬rable. In the case of bismuth the effect of complexation of Bi3+ by Cl- ions is appreciable for the higher chloride concentrations; the influence of the chloride ions on the reduction velocity thus results from a combination of its specific adsorption on the electrode and its tendency for complex formation. In the case of copper, only the specific adsorption of chloride ions is responsible for their effect on the electrode process kinetics since there is no complexation of the Cu2+ ion by Cl- in solution. For the reductions of bath bismuth and copper ions, a linear relation between the logarithms of the rate constants and the specifically adsorbed charge of Cl- ions is observed at constant potencial. These results agree with the theoretical models of PARSONS and of GUIDELLI and FORESTI describing the effect of non-electroactive, specifically adsorbed ions on the kinetics of electrode processes. The presence of specifically adsorbed charge, that depends on the electrode potential, explains the observed variation of the transfer coefficient as the concentration of the specifically adsorbed ion is increased. For copper, in which only apecific adsorption is responsible for the increase of the velocity, transfer coefficients corrected using the specific adsorption data are in agreement with the experimental results obtained from the variation of the logarithm of the rate constant with the potential.

Submitted by Fabricia Fialho Reginato (fabriciar) on 2015-06-27T00:47:04Z No. of bitstreams: 1 MarianaBattisti.pdf: 4940838 bytes, checksum: da6b432c65c732aae6b2315e828e6836 (MD5) / Made available in DSpace on 2015-06-27T00:47:04Z (GMT). No. of bitstreams: 1 MarianaBattisti.pdf: 4940838 bytes, checksum: da6b432c65c732aae6b2315e828e6836 (MD5) Previous issue date: 2013-03-27 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / FAPERGS - Fundação de Amparo à Pesquisa do Estado do Rio Grande do Sul / FINEP - Financiadora de Estudos e Projetos / O concreto é o material de construção mais empregado no mundo, consumindo grandes volumes de recursos naturais não renováveis, além da obtenção de matérias primas para sua produção causar grandes impactos ambientais. Deficiências do concreto relativas às propriedades de durabilidade podem diminuir a vida útil das estruturas, gerando resíduos precocemente, ou então necessitando de intervenções não previstas. A incorporação de agregados reciclados de concreto na produção de concreto vem sendo proposto como substituição parcial do agregado natural. No entanto, seu emprego pode aumentar a porosidade do concreto e diminuir sua durabilidade. A utilização de cinza de casca de arroz pode trazer melhorias nas propriedades dos concretos, principalmente quando se refere à penetração de íons cloreto e às propriedades mecânicas. O objetivo deste trabalho é avaliar a influência da cinza de casca de arroz na penetração de íons cloreto em concretos com agregado reciclado de concreto. Foram produzidos concretos com 0; 25 e 50% de agregado reciclado em substituição ao agregado natural; 0; 10 e 20% de substituição de cimento por cinza de casca de arroz; e relações água/aglomerante iguais a 0,42, 0,53 e 0,64. A resistência à compressão foi analisada aos 7, 28, 63 e 91 dias. Os ensaios de durabilidade englobaram os ensaios de absorção de água por capilaridade e dois métodos acelerados de penetração de íons cloretos: ASTM C1202 e NT Build 492, comumente empregados em pesquisas científicas. Os resultados mostram, em média, que a cinza de casca de arroz trouxe benefícios ao concreto com agregado reciclado de concreto em todas as propriedades estudadas. O comportamento observado pode ser atribuído a uma possível interação entre o agregado reciclado e o emprego da cinza de casca de arroz, em decorrência de uma reação pozolânica da cinza com produtos de hidratação da pasta do agregado reciclado e a um efeito microfíler da mesma nos poros deste agregado. O melhor desempenho foi obtido com concreto produzido com 50% de agregado reciclado de concreto e 20% de cinza de casca de arroz, com um aumento médio da resistência à penetração de íons cloreto de 91% pela ASTM C1202 e 64% pelo NT Build 492, em relação aos concretos de mesmo teor de agregado reciclado e sem cinza de casca de arroz. / The durability of building materials is emphasized when it searches to maintain the useful life of the construction design or extend it. Corrosion reinforcement in concrete is among one major problem that affects the constructions throughout the world. Chloride ion is one of the agents that can induce the corrosion reinforcement in concrete. For this reason, research about the durability of construction materials in severe environments gained space in the scientific community. The use of recycled concrete aggregate as replacement of natural aggregate has been studied to solve the question about non-renewable raw materials. But, these recycled waste as aggregate can increase the concrete porosity and reduce its durability. The rice husk ash has been employed as supplementary material in Portland cement concrete to get a more sustainable concrete and improve its durability, mainly related to chloride ingress. The aim of this research was to study the influence of rice husk ash on the chloride penetration in concrete made with recycled concrete aggregate. The natural coarse aggregates were replaced by recycled concrete aggregates in amounts of 0; 25 and 50%. The rice husk ash was employed as replacement of Portland cement in 0; 10 and 20%. Three water/binder ratios were used in concrete production: 0.42, 0.53 and 0.64. The compressive strength tests were conducted at 7, 28, 63 and 91 days age. The concrete resistance to chloride ingress was tested by the ASTM C1202 test method and by the NT Build 492 test method. The results of all studied properties showed that the use of rice husk ash can improve the concrete resistance against chloride ingress in concrete made with recycled concrete aggregate. This behavior can be attributed to the reduction of the porosity of recycled concrete aggregate due to interaction of rice husk ash with the calcium hydroxide of this aggregate as well as due to micro filler effect. The best performance was obtained in concrete with 50% of recycled concrete aggregate and 20% of rice husk ash. The resistance against chloride ingress in relation to the same concrete without rice husk ash was increased 91% in average when tested by ASTM C1202, and 64% when tested by NT Build 492.