O aumento de demanda por combustíveis menos poluentes e de fontes renováveis faz com que o Etanol se destaque como uma alternativa as fontes convencionais de energia. O crescente aumento no consumo deste produto, para os próximos anos, exigirá meios de transporte e estocagem eficientes e seguros, desde os diversos produtores até os terminais de distribuição. O transporte por dutos é, sem dúvida, a forma mais econômica de transporte deste produto, porém, há evidências de que esses dutos de transporte e fundo de tanques de armazenamento de etanol poderiam ser susceptíveis ao fenômeno de corrosão sob tensão. Este fenômeno pode ser avaliado, por exemplo, por ensaios de baixa taxa de deformação (BTD) com corpos de prova com ou sem entalhe. Este trabalho tem por objetivo avaliar a influência da severidade do entalhe em corpos de prova ensaiados a baixa taxa de deformação no meio etanol combustível simulado (PRCI SFGE). Foram preparados quatro tipos de corpos de prova de aço API X70: sem entalhe, com entalhe da norma NACE TM 0111, com entalhe “intermediário” (severidade 18,9% menor que o da norma) e com entalhe “menos severo” (redução de 37,2% na severidade do entalhe, segundo concentração de tensões, quando comparado com o da norma). Os resultados mostram que os quatro tipos de corpos de prova apresentaram susceptibilidade ao meio (etanol PRCI SFGE). Nos corpos de prova sem entalhe esta susceptibilidade foi evidenciada somente nas imagens fractográficas. Já nos CPs com entalhe, mesmo com redução de concentrações de tensões no entalhe, observou-se resultados bem semelhantes, ficando evidenciada a susceptibilidade ao meio tanto nas imagens fractográficas (fratura frágil), quanto pela diminuição da ductilidade. / The increasing demand for cleaner fuels and renewable sources makes the ethanol rise as an alternative to conventional energy sources. The increasing consumption rate of this product, predicted for the upcoming years, will require safer and more efficient methods for transportation and storage through the entire transport cycle. Pipelines are the most economical way to transport it. However, there is evidence that pipeline transportation and the bottom of the storage tanks for ethanol might be susceptible to the stress corrosion cracking phenomenon. This phenomenon can be assessed by slow strain rate tests (SSRT) using smooth or notched specimen. This work aims to evaluate the influence of notch severity in specimens submitted to SSRT technique in simulated fuelgrade ethanol (PRCI SFGE). Four types of specimens of steel API X70 were prepared: unnotched, notched according to standard NACE TM 0111, notched with “intermediate” severity (severity 18.9% lower than the standard) and “less severe” notched (reduction of 37.2% on severity of the notched when compared with the standard). The results show that both sample types presented susceptibility in the solution (ethanol PRCI SFGE). For the unnotched specimens this susceptibility was observed only in fractographic images. In the notched specimens, despite the reduction of stress concentrations in the notch, the results were very similar. In this case the susceptibility can be observed in fractographic images (brittle fracture) as well as by decrease in the ductility.

O aumento de demanda por combustíveis menos poluentes e de fontes renováveis faz com que o Etanol se destaque como uma alternativa as fontes convencionais de energia. O crescente aumento no consumo deste produto, para os próximos anos, exigirá meios de transporte e estocagem eficientes e seguros, desde os diversos produtores até os terminais de distribuição. O transporte por dutos é, sem dúvida, a forma mais econômica de transporte deste produto, porém, há evidências de que esses dutos de transporte e fundo de tanques de armazenamento de etanol poderiam ser susceptíveis ao fenômeno de corrosão sob tensão. Este fenômeno pode ser avaliado, por exemplo, por ensaios de baixa taxa de deformação (BTD) com corpos de prova com ou sem entalhe. Este trabalho tem por objetivo avaliar a influência da severidade do entalhe em corpos de prova ensaiados a baixa taxa de deformação no meio etanol combustível simulado (PRCI SFGE). Foram preparados quatro tipos de corpos de prova de aço API X70: sem entalhe, com entalhe da norma NACE TM 0111, com entalhe “intermediário” (severidade 18,9% menor que o da norma) e com entalhe “menos severo” (redução de 37,2% na severidade do entalhe, segundo concentração de tensões, quando comparado com o da norma). Os resultados mostram que os quatro tipos de corpos de prova apresentaram susceptibilidade ao meio (etanol PRCI SFGE). Nos corpos de prova sem entalhe esta susceptibilidade foi evidenciada somente nas imagens fractográficas. Já nos CPs com entalhe, mesmo com redução de concentrações de tensões no entalhe, observou-se resultados bem semelhantes, ficando evidenciada a susceptibilidade ao meio tanto nas imagens fractográficas (fratura frágil), quanto pela diminuição da ductilidade. / The increasing demand for cleaner fuels and renewable sources makes the ethanol rise as an alternative to conventional energy sources. The increasing consumption rate of this product, predicted for the upcoming years, will require safer and more efficient methods for transportation and storage through the entire transport cycle. Pipelines are the most economical way to transport it. However, there is evidence that pipeline transportation and the bottom of the storage tanks for ethanol might be susceptible to the stress corrosion cracking phenomenon. This phenomenon can be assessed by slow strain rate tests (SSRT) using smooth or notched specimen. This work aims to evaluate the influence of notch severity in specimens submitted to SSRT technique in simulated fuelgrade ethanol (PRCI SFGE). Four types of specimens of steel API X70 were prepared: unnotched, notched according to standard NACE TM 0111, notched with “intermediate” severity (severity 18.9% lower than the standard) and “less severe” notched (reduction of 37.2% on severity of the notched when compared with the standard). The results show that both sample types presented susceptibility in the solution (ethanol PRCI SFGE). For the unnotched specimens this susceptibility was observed only in fractographic images. In the notched specimens, despite the reduction of stress concentrations in the notch, the results were very similar. In this case the susceptibility can be observed in fractographic images (brittle fracture) as well as by decrease in the ductility.

O aumento de demanda por combustíveis menos poluentes e de fontes renováveis faz com que o Etanol se destaque como uma alternativa as fontes convencionais de energia. O crescente aumento no consumo deste produto, para os próximos anos, exigirá meios de transporte e estocagem eficientes e seguros, desde os diversos produtores até os terminais de distribuição. O transporte por dutos é, sem dúvida, a forma mais econômica de transporte deste produto, porém, há evidências de que esses dutos de transporte e fundo de tanques de armazenamento de etanol poderiam ser susceptíveis ao fenômeno de corrosão sob tensão. Este fenômeno pode ser avaliado, por exemplo, por ensaios de baixa taxa de deformação (BTD) com corpos de prova com ou sem entalhe. Este trabalho tem por objetivo avaliar a influência da severidade do entalhe em corpos de prova ensaiados a baixa taxa de deformação no meio etanol combustível simulado (PRCI SFGE). Foram preparados quatro tipos de corpos de prova de aço API X70: sem entalhe, com entalhe da norma NACE TM 0111, com entalhe “intermediário” (severidade 18,9% menor que o da norma) e com entalhe “menos severo” (redução de 37,2% na severidade do entalhe, segundo concentração de tensões, quando comparado com o da norma). Os resultados mostram que os quatro tipos de corpos de prova apresentaram susceptibilidade ao meio (etanol PRCI SFGE). Nos corpos de prova sem entalhe esta susceptibilidade foi evidenciada somente nas imagens fractográficas. Já nos CPs com entalhe, mesmo com redução de concentrações de tensões no entalhe, observou-se resultados bem semelhantes, ficando evidenciada a susceptibilidade ao meio tanto nas imagens fractográficas (fratura frágil), quanto pela diminuição da ductilidade. / The increasing demand for cleaner fuels and renewable sources makes the ethanol rise as an alternative to conventional energy sources. The increasing consumption rate of this product, predicted for the upcoming years, will require safer and more efficient methods for transportation and storage through the entire transport cycle. Pipelines are the most economical way to transport it. However, there is evidence that pipeline transportation and the bottom of the storage tanks for ethanol might be susceptible to the stress corrosion cracking phenomenon. This phenomenon can be assessed by slow strain rate tests (SSRT) using smooth or notched specimen. This work aims to evaluate the influence of notch severity in specimens submitted to SSRT technique in simulated fuelgrade ethanol (PRCI SFGE). Four types of specimens of steel API X70 were prepared: unnotched, notched according to standard NACE TM 0111, notched with “intermediate” severity (severity 18.9% lower than the standard) and “less severe” notched (reduction of 37.2% on severity of the notched when compared with the standard). The results show that both sample types presented susceptibility in the solution (ethanol PRCI SFGE). For the unnotched specimens this susceptibility was observed only in fractographic images. In the notched specimens, despite the reduction of stress concentrations in the notch, the results were very similar. In this case the susceptibility can be observed in fractographic images (brittle fracture) as well as by decrease in the ductility.

No description available.

In this work, Slow Strain Rate Test (SSRT) testing, Light Optical Microscopy (LOM) and Scanning Electron Microscopy (SEM) were used to study the effect of microstructure, corrosive environments and cathodic polarisation on stress corrosion cracking (SCC) of two grades of high strength steels, Type A and Type B. Type A is manufactured by quench and tempered (Q&T) method. Type B, a normalize steel was used as reference. This study also supports electrochemical polarisation resistance method as an effective testing technique for measuring the uniform corrosion rate. SSRT samples were chosen from base metal, weld metal and Heat Affected Zone (HAZ). SSRT tests were performed at room temperature under Open Circuit Potential (OCP) and cathodic polarisation using 4 mA/cm2 in 1 wt% and 3.5 wt% NaCl solutions. From the obtained corrosion rate measurements performed in 1 wt% and 3.5 wt% NaCl solutions it was observed that increased chloride concentration and dissolved oxygen content enhanced the uniform corrosion for all tested materials. Moreover, the obtained results from SSRT tests demonstrate that both Q&T and normalized steels were not susceptible to SCC in certain strain rate (1×10-6 s-1) in 1 wt% and 3.5 wt% NaCl solutions under OCP condition. It was confirmed by a ductile fracture mode and high reduction in area. The weld metal of Type A with acicular ferrite (AF), pro-eutectoid (PF) and bainite microstructure showed higher susceptibility to hydrogen assisted stress corrosion cracking compared to base metal and HAZ. In addition, typical brittle intergranular cracking with small reduction in area was observed on the fracture surface of the Type A due to hydrogen charging.

Um dos principais mecanismos de falha que causam riscos de fratura a reatores de água pressurizada é a corrosão sob tensão de ligas metálicas em água do circuito primário (CSTAP). É causada por uma combinação das tensões de tração, meio ambiente em temperatura e microestruturas metalúrgicas susceptíveis. Ela pode ocorrer, dentre outros locais, nos bocais do mecanismo de acionamento das barras de controle. Essa fratura pode causar acidentes que comprometem a segurança nuclear através do bloqueio das barras de controle e vazamentos de água do circuito primário reduzindo a confiabilidade e a vida útil do reator. O objetivo desta Tese de Doutorado é o estudo de modelos e uma proposta de modelagem para fraturas por corrosão sob tensão em liga 75Ni15Cr9Fe (liga 600), em água de circuito primário de reator de água pressurizada nesses bocais. São superpostos modelos eletroquímicos e de mecânica da fratura e validados com dados obtidos em experimentos e na literatura. Na parte experimental foram utilizados resultados obtidos pelo CDTN no equipamento recém-instalado de ensaio por taxa de deformação lenta. Na literatura está proposto um diagrama que exprime a condição termodinâmica de ocorrerem diversos modos de CSTAP na liga 600: partiu-se de diagramas de potencial x pH (diagramas de Pourbaix), para a liga 600 imersa em água primária à alta temperatura (3000C a 3500C). Sobre ele, determinaram-se os submodos de corrosão, a partir de dados experimentais. Em seguida acrescentou-se uma dimensão adicional ao diagrama, correlacionando uma variável a que se denominou fração de resistência à corrosão sob tensão. No entanto, é possível acrescentar-se outras variáveis que exprimem a cinética de iniciação e/ou crescimento de trinca, provenientes de outras modelagens de CSTAP. A contribuição original deste trabalho se insere nessa fase: partindo-se de uma condição de ensaio de potencial versus pH, foram iniciadas as modelagens de um modelo empírico-comparativo, um semi-empírico-probabilístico, um de tempo de iniciação e um de taxa de deformação, a partir dos ensaios experimentais e superpostas a essa condição. Esses exprimem respectivamente a susceptibilidade à CSTAP, o tempo de falha, e nos dois últimos o tempo de iniciação de falha por corrosão sob tensão. Os resultados foram comparados com os da literatura e se mostraram coerentes. Através desse trabalho, obteve-se uma metodologia de modelagem a partir de dados experimentais. / One of the main failure mechanisms that cause risks to pressurized water reactors is the primary water stress corrosion cracking (PWSCC) occurring in alloys. It can occurs, besides another places, at the control reactor displacement mechanism nozzles. It is caused by the joint effect of tensile stress, temperature, susceptible metallurgical microstructure and environmental conditions of the primary water. These cracks can cause accidents that reduce nuclear safety by blocking the rods displacement and may cause leakage of primary water, reducing the reactors life. In this work it is proposed a study of the existing models and a modeling proposal to primary water stress corrosion cracking in these nozzles in a nickelbased Alloy 600. It is been superposed electrochemical and fracture mechanics models, and validated using experimental and literature data. The experimental data were obtained at CDTN-Brazilian Nuclear Technology Development Center, in a recent installed slow strain rate testing equipment. In the literature it is found a diagram that indicates a thermodynamic condition for the occurrence of some PWSCC submodes in Alloy 600: it was used potential x pH diagrams (Pourbaix diagrams), for Alloy 600 in high temperature primary water (3000C till 3500C). Over it, were located the PWSCC submodes, using experimental data. It was added a third parameter called stress corrosion strength fraction. However, it is possible to superpose to this diagram, other parameters expressing PWSCC initiation or growth kinetics from other models. Here is the proposition of the original contribution of this work: from an original experimental condition of potencial versus pH, it was superposed, an empiric-comparative, a semi-empiric-probabilistic, an initiation time, and a strain rate damage models, to quantify respectively the PWSCC susceptibility, the failure time, and in the two lasts, the initiation time of stress corrosion cracking. It was modeling from our experimental data. The results were compared with the literature and it showed to be coherent. From this work was obtained a modeling methodology from experimental data.

In recent years, the demand for alternatives to fossil fuels has risen dramatically, and ethanol fuel has become an important liquid fuel alternative globally. The most efficient mode of transportation of petroleum-based fuel is via pipelines, and due to the 300% increase in ethanol use in the U.S. in the past decade, a similar method of conveyance must be adopted for ethanol. Low-carbon, low-alloy pipeline steels like X52, X60, and X65 comprise the existing fuel transmission pipeline infrastructure. However, similar carbon steels, used in the ethanol processing and production industry, were found to exhibit stress corrosion cracking (SCC) in ethanol service. Prior work has shown that contaminants absorbed by the ethanol during distillation, processing or transport could be the possible determinants of SCC susceptibility; 200 proof ethanol alone was shown not to cause SCC in laboratory studies. To ensure the safety and integrity of the pipeline system, it was necessary to perform a mechanistic study of SCC of pipeline steel in fuel grade ethanol (FGE). The objective of this work was to determine the environmental factors relating to SCC of X65 steel in fuel grade ethanol (FGE) environments. To accomplish this, a systematic study was done to test effects of FGE feedstock and common contaminants and constituents such as water, chloride, dissolved oxygen, and organic acids on SCC behavior of an X65 pipeline steel. Slow strain rate tests (SSRT) were employed to evaluate and compare specific constituents' effects on crack density, morphology, and severity of SCC of X65 in FGE. SCC did not occur in commercial FGE environments, regardless of the ethanol feedstock. In both FGE and simulated fuel grade ethanol (SFGE), SCC of carbon steel was found to occur at low water contents (below 5 vol%) when chloride was present above a specific threshold quantity. Cl- threshold for SCC varied from 10ppm in FGE to approximately 1 ppm in SFGE. SCC of carbon steel was inhibited when oxygen was removed from solution via N2 purge or pHe was increased by addition of NaOH. During SSRT, in-situ¬ electrochemical measurements showed a significant role of film rupture in the SCC mechanism. Analysis of repassivation kinetics in mechanical scratch tests revealed a large initial anodic dissolution current spike in SCC-causing environments, followed by repassivation indicated by current transient decay. In the deaerated environments, repassivation did not occur, while in alkaline SFGE repassivation was significantly more rapid than in SCC-inducing SFGE. Composition and morphology of the passive film on X65 during static exposure tests was studied using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Results showed stability of an air-formed native oxide under static immersion in neutral (pHe = 5.4) SFGE, and dissolution of the film when pHe was decreased to 4.3. XPS spectra indicated changes in film composition at high pHe (near 13) and in environments lacking sufficient water. In light of all results, a film-rupture anodic-dissolution mechanism is proposed in which local plastic strains facilitates local breakdown of the air-formed oxide film, causing iron to dissolve anodically. During crack propagation anodic dissolution occurs at the crack tip while crack walls repassivate preserving crack geometry and local stress concentration at the tip. It is also proposed that SCC can be mitigated by use of alkaline inhibitors that speed repassivation and promotes formation of a more protective Fe(OH)3 film.

Um dos principais mecanismos de falha que causam riscos de fratura a reatores de água pressurizada é a corrosão sob tensão de ligas metálicas em água do circuito primário (CSTAP). É causada por uma combinação das tensões de tração, meio ambiente em temperatura e microestruturas metalúrgicas susceptíveis. Ela pode ocorrer, dentre outros locais, nos bocais do mecanismo de acionamento das barras de controle. Essa fratura pode causar acidentes que comprometem a segurança nuclear através do bloqueio das barras de controle e vazamentos de água do circuito primário reduzindo a confiabilidade e a vida útil do reator. O objetivo desta Tese de Doutorado é o estudo de modelos e uma proposta de modelagem para fraturas por corrosão sob tensão em liga 75Ni15Cr9Fe (liga 600), em água de circuito primário de reator de água pressurizada nesses bocais. São superpostos modelos eletroquímicos e de mecânica da fratura e validados com dados obtidos em experimentos e na literatura. Na parte experimental foram utilizados resultados obtidos pelo CDTN no equipamento recém-instalado de ensaio por taxa de deformação lenta. Na literatura está proposto um diagrama que exprime a condição termodinâmica de ocorrerem diversos modos de CSTAP na liga 600: partiu-se de diagramas de potencial x pH (diagramas de Pourbaix), para a liga 600 imersa em água primária à alta temperatura (3000C a 3500C). Sobre ele, determinaram-se os submodos de corrosão, a partir de dados experimentais. Em seguida acrescentou-se uma dimensão adicional ao diagrama, correlacionando uma variável a que se denominou fração de resistência à corrosão sob tensão. No entanto, é possível acrescentar-se outras variáveis que exprimem a cinética de iniciação e/ou crescimento de trinca, provenientes de outras modelagens de CSTAP. A contribuição original deste trabalho se insere nessa fase: partindo-se de uma condição de ensaio de potencial versus pH, foram iniciadas as modelagens de um modelo empírico-comparativo, um semi-empírico-probabilístico, um de tempo de iniciação e um de taxa de deformação, a partir dos ensaios experimentais e superpostas a essa condição. Esses exprimem respectivamente a susceptibilidade à CSTAP, o tempo de falha, e nos dois últimos o tempo de iniciação de falha por corrosão sob tensão. Os resultados foram comparados com os da literatura e se mostraram coerentes. Através desse trabalho, obteve-se uma metodologia de modelagem a partir de dados experimentais. / One of the main failure mechanisms that cause risks to pressurized water reactors is the primary water stress corrosion cracking (PWSCC) occurring in alloys. It can occurs, besides another places, at the control reactor displacement mechanism nozzles. It is caused by the joint effect of tensile stress, temperature, susceptible metallurgical microstructure and environmental conditions of the primary water. These cracks can cause accidents that reduce nuclear safety by blocking the rods displacement and may cause leakage of primary water, reducing the reactors life. In this work it is proposed a study of the existing models and a modeling proposal to primary water stress corrosion cracking in these nozzles in a nickelbased Alloy 600. It is been superposed electrochemical and fracture mechanics models, and validated using experimental and literature data. The experimental data were obtained at CDTN-Brazilian Nuclear Technology Development Center, in a recent installed slow strain rate testing equipment. In the literature it is found a diagram that indicates a thermodynamic condition for the occurrence of some PWSCC submodes in Alloy 600: it was used potential x pH diagrams (Pourbaix diagrams), for Alloy 600 in high temperature primary water (3000C till 3500C). Over it, were located the PWSCC submodes, using experimental data. It was added a third parameter called stress corrosion strength fraction. However, it is possible to superpose to this diagram, other parameters expressing PWSCC initiation or growth kinetics from other models. Here is the proposition of the original contribution of this work: from an original experimental condition of potencial versus pH, it was superposed, an empiric-comparative, a semi-empiric-probabilistic, an initiation time, and a strain rate damage models, to quantify respectively the PWSCC susceptibility, the failure time, and in the two lasts, the initiation time of stress corrosion cracking. It was modeling from our experimental data. The results were compared with the literature and it showed to be coherent. From this work was obtained a modeling methodology from experimental data.

In this work, Slow Strain Rate Test (SSRT) testing, Light Optical Microscopy (LOM) and Scanning Electron Microscopy (SEM) were used to study the effect of microstructure, corrosive environments and cathodic polarisation on stress corrosion cracking (SCC) of two grades of high strength steels, Type A and Type B. Type A is manufactured by quench and tempered (Q&T) method. Type B, a normalize steel was used as reference. This study also supports electrochemical polarisation resistance method as an effective testing technique for measuring the uniform corrosion rate. SSRT samples were chosen from base metal, weld metal and Heat Affected Zone (HAZ). SSRT tests were performed at room temperature under Open Circuit Potential (OCP) and cathodic polarisation using 4 mA/cm2 in 1 wt% and 3.5 wt% NaCl solutions. From the obtained corrosion rate measurements performed in 1 wt% and 3.5 wt% NaCl solutions it was observed that increased chloride concentration and dissolved oxygen content enhanced the uniform corrosion for all tested materials. Moreover, the obtained results from SSRT tests demonstrate that both Q&T and normalized steels were not susceptible to SCC in certain strain rate (1×10-6 s-1) in 1 wt% and 3.5 wt% NaCl solutions under OCP condition. It was confirmed by a ductile fracture mode and high reduction in area. The weld metal of Type A with acicular ferrite (AF), pro-eutectoid (PF) and bainite microstructure showed higher susceptibility to hydrogen assisted stress corrosion cracking compared to base metal and HAZ. In addition, typical brittle intergranular cracking with small reduction in area was observed on the fracture surface of the Type A due to hydrogen charging.