Made available in DSpace on 2014-10-09T12:41:49Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:17Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:41:49Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:17Z (GMT). No. of bitstreams: 0 / Cerâmicas de zircônia estabilizada com ítria são utilizadas na forma densa como eletrólito e na forma porosa como ânodo em células a combustível de óxido sólido. Neste trabalho cerâmicas porosas de zircônia estabilizada com 8 mol% de ítria foram preparadas por meio da adição de diferentes teores de KI, NaCl e grafite como aditivo sacrificial. A remoção térmica do aditivo foi avaliada por meio de análises termogravimétrica, térmica diferencial e dilatométrica. As amostras foram preparadas por meio de mistura, compactação e sinterização a 1400 ºC/2 h. As amostras foram caracterizadas por difração de raios X(DRX) e análise topográfica em microscópio de varredura por sonda e microscópio eletrônico de varredura de superfícies polidas e atacadas para avaliação da distribuição do teor de poros e tamanho médio de grãos. O teor do aditivo residual foi avaliado por fluorescência de raios X (FRX). O comportamento elétrico foi analisado por espectroscopia de impedância (EI) na faixa de frequências 5 Hz-10 MHz entre 300 ºC e 450 ºC. Os resultados de FRX mostram que não há resíduo do aditivo após sinterização. A análise de DRX indica que todas as amostras têm fase única, cúbica tipo fluorita. Os diagramas de impedância mostram que há aumento i) das resistividades elétricas intergranular e intragranular, evidenciando a formação de poros em ambas as regiões, ii) do ângulo de descentralização do semicírculo a baixas frequências, devido ao aumento do grau de heterogeneidade pela presença de poros, e iii) do produto do fator de bloqueio R pelo fator de frequência f, consequência do aumento do teor de poros. Esses resultados estão em concordância com os resultados das análises de microscopia de varredura por sonda e de microscopia eletrônica de varredura. / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-22T16:42:40Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-22T16:42:40Z (GMT). No. of bitstreams: 0 / Neste trabalho foi estudado o efeito da adição de íons haletos (Cl-, Br- e I-) sobre a morfologia das nanopartículas de Pt na produção de catalisadores de Pt/C e PtSnO2/C. Foi desenvolvida uma metodologia de síntese simples capaz de produzir nanopartículas de Pt predominantemente cúbicas com orientação preferencial Pt(100), diretamente suportadas em carbono sem o uso de agentes estabilizantes. Brometo de potássio foi utilizado como agente direcionador de superfície para obtenção do material preferencialmente orientado. O controle de adição do precursor de Pt e de KBr foi crucial para obter nanocubos de Pt de 8 nm bem dispersos sobre o suporte. Na preparação dos catalisadores de PtSnO2/C, o processo de adição do SnCl2 também foi decisivo na obtenção das nanopartículas de Pt com tamanho e morfologia de interesse. Nanocubos de Pt coexistindo com SnO2 disperso foram exclusivamente obtidos ao adicionar o SnCl2 na etapa final da síntese, quando as nanopartículas cúbicas de Pt já estavam formadas. Enriquecidos de domínios Pt(100), os materiais em forma cúbica de Pt/C e PtSnO2/C se mostraram menos afetados pelo acúmulo dos intermediários indesejados provenientes da reação de eletro-oxidação de etanol e foram mais tolerantes ao envenenamento por monóxido de carbono. Resultados similares foram observados para a oxidação de CO e metanol, utilizados como apoio para compreensão da eletro-oxidação de etanol. O efeito morfológico destes materiais no desempenho elétrico em célula a combustível de etanol direto foi avaliado. Pt/C e PtSnO2/C contendo nanopartículas de Pt com orientação preferencial Pt(100) forneceram maiores valores de densidade de potência e de seletividade para CO2 comparados aos catalisadores de Pt/C e PtSnO2/C com nanopartículas de Pt sem orientação preferencial. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

A corrosão de armaduras é uma das causas mais comuns de degradação mecânica em estruturas em concreto armado. Esse processo leva à redução da vida útil e, consequentemente, a prejuízos econômicos. Desse modo, o presente trabalho visa contribuir com a análise dos fenômenos associados à degradação mecânica do concreto armado sujeito a processos corrosivos devido à carbonatação e à ação de cloretos. Para tal finalidade, modelos analíticos baseados na segunda lei de Fick são usados para quantificar a difusão de CO2 e de íons cloreto no concreto, os quais permitem determinar o tempo de início da corrosão. A degradação mecânica de estruturas em concreto armado é considerada por meio de um modelo em dano concentrado que contempla perda da rigidez, redução da área de aço e da tensão de escoamento de armaduras devido ao processo corrosivo. A formulação de dano concentrado foi modificada de forma a incluir uma variável de estado de corrosão e uma lei de evolução da corrosão, baseada em equações semi-empíricas disponíveis na literatura. Essas equações determinam a redução no diâmetro das armaduras e a perda da capacidade resistente do aço. O problema da corrosão é formulado como um processo estocástico sendo resolvido por meio do método de simulação de Monte Carlo para dois exemplos: uma viga isostática e um pórtico plano com grau de hiperestaticidade igual a três. A formulação da equação de estado limite é baseada em um valor de dano aceitável. Curvas de probabilidade de início da corrosão e de probabilidade de falha da estrutura são obtidas ao longo de 50 anos. No caso da estrutura hiperestática, o caminho mais provável de falha, também chamado de caminho crítico, é determinado. Observa-se que o processo corrosivo provoca mudanças no caminho crítico, e portanto, deve ser considerado nas análises de reparo estrutural. Mapas de dano e de probabilidade de falha foram desenvolvidos para mostrar as mudanças no comportamento estrutural devido à corrosão. / The reinforcement\'s corrosion is one of the most common causes of mechanical degradation in reinforced concrete structures. This process leads to the reduction of the service life and, consequently, economic loss. Thereby, this study aims to contribute with the analysis of the phenomena associated to the mechanical degradation of reinforced concrete, due to the carbonation and the chloride ions. For this purpose, analytical models based on second Fick\'s law are used to quantify CO2 and chloride ions diffusion, which enables to determine the corrosion time initiation. The mechanical degradation of reinforced concrete structures is modeles by the lumped damage model which accounts for stiffness loss, reinforcement mass loss and yield stress reduction due to the corrosive process. The lumped damage formulation was modified to include the state corrosion variable and the corrosion evolution law based on semi-empirical equations available in the literature. These equations determine the reinforcement\'s diameter reduction and the loss of resistant capacity of the reinforcement\'s bar. The corrosion problem is formulated as a stochastic process and solved by the Monte Carlo simulation for two examples: an isostatic beam and a hyperstatic frame. The limit state functions are based on the acceptable damage value. Curves of probability of corrosion initiation and probability of failure are obtained over a range of 50 years. In the hyperstatic case, the most probable failure path, also named the critical path, is determined. It is observed that the corrosive process causes changes on the critical path and, therefore, it must be accounted on structural repair analysis. Damage and probability of failure maps were developed to show the changes on the structural behavior due to the corrosion.

En raison de leurs excellentes propriétés mécaniques, couplées à une bonne résistance à la corrosion par piqûres et à un coût modéré (basse teneur en nickel et en molybdène), les aciers inoxydables austéno-ferritiques (dits aciers inoxydables duplex) sont largement utilisés dans de nombreux secteurs industriels. Les aciers inoxydables duplex ont une microstructure complexe composée à proportion équivalente d’austénite et de ferrite. L’austénite ayant une composition chimique différente de celle de la ferrite, un film hétérogène se forme à la surface des aciers inoxydable duplex. Par ailleurs, les deux phases métalliques ayant des propriétés mécaniques différentes, un champ de contraintes hétérogènes est généré dans les grains. Sous certaines conditions, l’existence de gradients de contraintes peut conduire à des hétérogénéités du film passif. Dans cette étude, l’effet d’un vieillissement de longue durée dans un milieu contenant des chlorures sur la composition chimique du film passif a été tout d’abord étudié. Le comportement en corrosion de certains alliages duplex a été ensuite déterminé à partir d’essais TCP (détermination de la température critique de piqûration). Les résultats ont été analysés en tenant compte des informations obtenues précédemment. Après vieillissement, l’épaisseur du film passif et le rapport Cr/Fe ont significativement augmenté. La distribution des chlorures dans le film passif est hétérogène. Cette distribution a été reliée à la microstructure du matériau et au champ de contraintes résiduelles. Il a été montré qu’elle influence le comportement électrochimique du matériau. Le comportement en corrosion est ensuite analysé à l’aide des courbes de polarisation locales. Des critères métallurgiques ont été proposés pour l’amorçage de piqûres. / Duplex stainless steels (DSS) are highly important engineering materials, due to their generally high corrosion resistance combined with high strength and moderate alloy cost (lower nickel and molybdenum content). They are widely used in various industrial sectors. DSS have a complex microstructure with comparable volume of austenite and ferrite. Due to differences in chemical composition between austenite and ferrite, a heterogeneous passive film is formed on both phases. In addition, due to differences in mechanical properties, a heterogeneous stress field may be generated in metallic grains. Under certain conditions, these differences may also yield formation of a heterogeneous passive film. In this work, the influence of long-term ageing in chloride-containing media by on the chemical composition of the passive film was first studied by means of XPS and Auger at the microscale. The corrosion behaviour of some duplex stainless steels was then determined from CPT tests (determination of the critical pitting temperature). Results were analysed taking into account information obtained previously. After ageing, the thickness and the ratio Cr/Fe are significantly increased. The chloride distribution in the passive film was heterogeneous. It was related to the microstructure and the residual strain field. It was shown that this distribution modifies the electrochemical behaviour of samples. The corrosion behaviour was then analysed from local polarization curves and CPT tests. Metallurgical criteria for pitting were proposed.

Chlorine solid-state nuclear magnetic resonance (SSNMR) is an ideal site specific probe of chloride-containing solids as SSNMR tensor properties are sensitive to the local chlorine environment. In this thesis, the development and use of chlorine SSNMR as a method to characterize a wide variety of chemical environments was explored. Ultrahigh field, and multi-field studies were essential to overcome the difficulties associated with the collection of chlorine SSNMR spectra. Benchmark chemical shift (CS) and electric field gradient (EFG) tensor data were collected for organic chloride systems, including several amino acid hydrochlorides. These experiments demonstrated the sensitivity of chlorine SSNMR to slight changes in chemical environment. Quantum chemical calculations were used to complement experimental data, with the gauge-including projector augmented wave DFT (GIPAW-DFT) method shown to yield better agreement than B3LYP or RHF methods. The GIPAW-DFT method was found to slightly, but systematically, overestimate the chlorine quadrupolar coupling constant and the CS tensor span. Other organic chlorides examined by chlorine SSMR included a known ion receptor, meso-octamethylcalix[4]pyrrole. This compound was found to have a very small quadrupole interaction (QI), but significant chemical shift anisotropy (CSA). GIPAW-DFT calculations were also utilized and, in combination with the experimental results, used to identify the solvate structure of the material analyzed by NMR. Chlorine SSNMR was further used to study different solvate structures and polymorphism. The technique was an effective means to distinguish different room temperature polymorphs of benzidine hydrochloride, despite the similarities of the chloride environments. In the case of magnesium chloride, chlorine SSNMR was sensitive to the level of hydration and through the use of GIPAW-DFT calculations, the identity of an unknown hydrate was determined. An analysis of several group thirteen chlorides demonstrated that chlorine SSNMR was also capable of characterizing the chlorine environment in cases where the QI is large, despite the resulting broad line widths. In these systems GIPAW-DFT calculations also yielded excellent agreement with experimental values. Throughout this research, chlorine SSNMR has been shown to be a useful and effective means to study both organic and inorganic chlorides, with computational methods proving to be an important complement to experimental data.

From August 1996 through September 1997 eleven fixed stations were sampled monthly in January, March , April , July, August, September, and November and fortnightly in May and June for the purposes of establishing baseline conditions present in Lake Texoma as related to U.S. Army Corps of Engineers chloride control activities in the upper Wichita River, Texas. Five reservoir zones were identified a priori using historical chloride concentration data and include the Red River Zone (RRZ), Red River Transition Zone (RRTZ), Main Lake Body (MLB), Washita River Transition Zone (WRTZ), and Washita River Zone (WRZ) in order of decreasing chloride concentration. The existence of the WRTZ is not supported here, however the Big Mineral Arm in the RRTZ was observed to be highly independent of the mixing patterns observed in the RRTZ and was treated post priori separately from the RRTZ. Spatial and temporal comparisons between reservoir zones were performed on seventeen (17) physicochemical parameters from each of the eleven sampling stations and phytoplankton count data from one sampling station within each reservoir zone and physicochemical parameters were observed to exhibit a fixed spatial gradient. Strong density gradients throughout the reservoir were observed to occur in conjunction with vertical stratification of the water column. Stratification stability at individual stations was attributable to both thermal and salinity density gradients throughout the period of stratification with the degree to which stratification is thermally or chemically induced influenced by inter-annual variability in hydraulic residence time. Hypolimnetic oxygen depletion rates were also observed to be affected by changes in hydraulic residence time with a long-term trend of decreasing relative areal hypolimnetic oxygen rates detected between the 1970s and 1990s. The algal assemblage present in Lake Texoma is dominated by the Cyanophyta, which comprises 82.1 % of the assemblage total standing crop with one species, Microcystis incerta, comprising 57.0 % of the assemblage total standing crop and is typical of a temperate eutrophic lake. The algal assemblage was affected more by temporal dynamics rather than spatial dynamics with variance observed in the algal assemblage attributable to physicochemical factors which vary through time.

Made available in DSpace on 2017-06-01T17:57:32Z (GMT). No. of bitstreams: 1 Ronaldo Pontes.pdf: 4668306 bytes, checksum: 48d4fe1ec07bae512f5d789ae55d9ec8 (MD5) Previous issue date: 2006-03-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Exposing concrete structures to the saline mist, they can suffer chlorides attacks and could cause reinforcement corrosion. The structures parts with faces directed to dominant winds are more susceptible, especially those with great surface in relation to the volume, such as pillars and beams. This work objective is to evaluate the level of marine aggressiveness, in marine edge of Boa Viagem quarter, Recife-PE, in function of the distance to the sea, measuring the value of chloride deposition, using the wet candle method, with the support of the environment management. The results indicate that chloride ions reach surface structure in different levels of concentration, depending on the distance from its origin, in this case, the sea. The conclusion is that chloride deposition decreases, in an exponential relation, when there is an increase of the distance to the sea, and that aggressiveness is significantly as far as 400 m from the marine edge / Diante da exposição à névoa salina, as estruturas em concreto podem sofrer ataques por cloretos, provocando corrosão das armaduras. As peças com faces voltadas aos ventos dominantes estão mais suscetíveis, especialmente aquelas que possuem grande superfície em relação ao volume, como são os casos de pilares e vigas. Este trabalho tem como objetivo avaliar os níveis de agressividade marinha, na orla marítima do Bairro de Boa Viagem, Recife-PE, em função de sua distância em relação ao mar, medindo a taxa de deposição de cloretos, pelo método da vela úmida, tendo como apoio o monitoramento do ambiente. Os resultados indicam que os íons cloreto chegam à superfície das estruturas a distintos níveis de concentração, dependendo da distância em relação à sua fonte geradora, no caso, o mar. Conclui-se que a deposição de cloretos decresce, numa relação do tipo exponencial, à medida que há um aumento do distanciamento em relação ao mar, e que a agressividade é significativa até 400 m da orla marítima

Submitted by Biblioteca Central (biblioteca@unicap.br) on 2018-04-11T18:44:16Z No. of bitstreams: 2 adriana_maria_monteiro_passos.pdf: 4108061 bytes, checksum: 98b74cf5e2d768af7917f11d7e580f90 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-04-11T18:44:16Z (GMT). No. of bitstreams: 2 adriana_maria_monteiro_passos.pdf: 4108061 bytes, checksum: 98b74cf5e2d768af7917f11d7e580f90 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2013-06-03 / Urban concrete or reinforced concrete structures built in saline environments, under either intermittent or continuous sea water exposure, usually present mechanical wear and structure pathology problems that require relentless maintenance care. Currently, Brazil has a large number of civil construction equipment and buildings under direct or near direct contact with the sea and the city of Recife, Pernambuco State capital, for one, figures among the top most exposed cities in terms of number of urban equipment in contact with sea water, including buildings, bridges, mooring sites, footbridges, piers, i.e., design projects that essentially imply concrete structures located under diverse marine exposure conditions such as underwater or partially submersed structures, or structures located in tidal zones or areas under mist or sea water splash environments. Sea water carries rather high chloride ion contents, hence making those exposed structures especially vulnerable. A chloride penetration study was carried out according to ISO TC 71/SC 1 (07/26/2010 release), ISO/WD 1920-11, ISO TC 71/SC 1/WG SII, and Brazilian ABNT NBR 12655 standards. Concrete core samples of several strength levels were kept partially submerged in sea water; chloride ion contents and penetration depths were recorded. Furthermore, a number of chemical analyses have been conducted in order to estimate chloride contents present at several depths in various concrete samples prepared with several W/C ratios, hence with different strength values. According to what one might expect, laboratory assays indicated that the deeper the axial sample taken from the exposed core for analysis and the more concentrated the concrete Water/Cement ratio, the lower the chloride penetration. Therefore, the chloride ion penetration rate indeed decreases as the W/C ratio gets richer, when compared to average and poor W/C ratios for all sampled penetration depths analyzed. / Em cidades que estão sujeitas a essa exposição salina, as construções de concreto ou concreto armado, ora em contato com água do mar ora não, ou à vontade dos mares sempre sofrem patologias e desgastes mecânicos; que exigem permanente manutenção. O Brasil atualmente; possuí vários equipamentos e construções que estão em contato direto ou semidireto com o mar. Recife capital de Pernambuco, é uma das cidades que mais tem equipamentos urbanos em contato com a água do mar. Edifícios, pontes, ancoradouros, passarelas, piers, enfim projetos que determinam estruturas em concreto em ambiente marítimo: ambientes de zona submersa, parcialmente submersa, zona de maré, zona de respingo e zona de névoa. As águas do mar contem elevada quantidade de íons de cloretos; e essa exposição torna mais vulnerável essas estruturas de concreto. Esta dissertação pesquisou e estudou a penetração de cloretos, de acordo com parametros da ISO TC 71/SC 1 de 26/07/2010, ISO/WD 1920-11, ISO TC 71/SC 1/WG SII, e a ABNT NBR 12655, experimentando corpos de prova de concreto, de diferentes resistèncias que ficaram parcialmente imersos em água do mar; verificando quantidade e a profundidade de penetração de íons de cloretos. Portanto, o principal objetivo deste trabalho foi, através de ensaios quimicos, a definição do quantitativo de íons de cloretos em exemplares com concreto de traços de diferentes resistências, à diferentes profundidades. De acordo com as expectativas, verificou-se com os ensaios em laboratórios que quanto e mais rico o traço de concreto, acontece menor quantidade de penetração de íons de cloretos. Portanto se pode dizer que o percentual de penetração de íons cloreto é menor para o traço rico, em relação ao traço médio e o pobre em todas as perfurações feitas nos corpos de prova estudados.

Parkeringsanläggningar utsätts ständigt av belastningar från körande fordon och kloridangrepp under vinterperioden. Påföljden av det blir kostsamma skador på betongkonstruktionen, främst vid uppkomna sprickor. Kloridinträngning medför att armeringsjärnen korroderar och försvagar underliggande betongkonstruktionen. Ersättning av de korroderade armeringsjärnen samt betonglagningar är kostsamt för Stockholm Parkering. Lösningen är att förbehandla den oskyddade betongen och applicera en ytbeläggning ovanför. De vanligaste som finns i Sverige är cementbaserade, bitumenbaserade och härdplastbaserade ytbeläggningar. Det finns inga direktiv för val när det gäller ytbeläggningar. Eftersom alla ytbeläggningar har olika egenskaper är det för- och nackdelar som beställaren ska värdera beroende på parkeringshusets förutsättningar som utformningen, trafikbelastningen och om det är grundplattan eller mellanbjälklaget som ytbeläggningen appliceras på. Förutom materialet är utförandet också viktigt. En väl utförd förbehandling av betongunderlaget och noggrann utläggning av ytbeläggningen minskar risken för uppkomst av skador i framtiden och därmed reparationskostnaderna. Syftet med examensarbetet är att undersöka olika ytbeläggningar som har varit i drift 5 till 10 år för att sedan identifiera och kartlägga skador som har uppkommit på dem. I denna rapport har fem parkeringsanläggningar valts ut som fallstudier för att undersöka de vanligaste ytbeläggningarna som används idag i Stockholm Parkerings parkeringsanläggningar. Utifrån litteraturstudier, intervjuer med olika parter i respektive projekt, observationer som utfördes under studiebesöken och jämförelse mellan fallstudier dras slutsatser för att hitta den hållbaraste ytbeläggningen. Slutligen skapas en lathund för att förenkla valet av ytbeläggningar för parkeringsanläggningar med olika förutsättningar. / Parking facilities are constantly exposed to traffic loads from driving vehicles and chloride attacks during the winter period. The consequence of this is costly damage to the concrete structure, especially in the event of cracks. Chloride penetration causes the reinforcement bars to corrode and weaken the underlying concrete structure. Replacement of the corroded reinforcement bars and concrete repairs are costly for Stockholm Parking. The solution is to pretreat the unprotected concrete and apply a coating above it. The most common coatings found in Sweden are cement-based, bitumen-based and thermoset-based coatings. There is no clear choice when it comes to coatings since they all have different properties. The advantages and disadvantages of different coatings that the customer must value depend on such conditions of the parking garage as the shaping, the traffic load and whether it is the base plate or the intermediate floor. Besides the material, the execution is also important. A well done pretreatment of the concrete substrate and meticulous laying of the coating reduces the possibility of the occurrence of damage in the future and thereby the repair costs. The purpose of the thesis project was investigation of various coatings systems that have been in operation for 5 to 10 years and identification and mapping damages that occur to them. In this report, five parking facilities have been selected as case studies to investigate the most common coatings used today in Stockholm Parkering parking facilities. Based on literature studies, interviews with various parties in each project, observations made on study visits and comparison between case studies conclusions were drawn about the most sustainable surface coating systems. Finally, a guidance is created to simplify the choice of coating systems for parking facilities with different conditions.