In this research, the corrosion performance of two austenitic stainless steels, namely 316L and 254SMO, in concentrated acetic acid solutions containing bromide ions has been investigated. In this research, the influence of two different electrochemical surface treatments (electropolishing and nitric acid passivation) on the corrosion behaviour of 316L stainless steel immersed in 15.3M HAc with 18.7mM bromide ions at 900°C was examined. Also, attemptswere made to study the performance of three organic inhibitors in the same conditions. Corrosion rates are assessed both by weight loss, and linear polarisation resistance. Interfacial corrosion chemistry is further characterised by open circuit potential and potentiodynamic polarization measurements. Substrate morphology is elucidated with optical microscopy, including 3D surface profiling, and scanning electron microscopy. Also, X-ray photoelectron spectroscopy is employed to gain further insight into the quite differentcorrosion performances of 316L and 254SMO in 15.3M acetic acid with 18.7mM Br ions.It was found that 316L and 254SMO steels have good corrosion resistance and low corrosion rates in 11.9M-HAc-Br-. Increasing acid concentration to 15.3 M led to a dramatic increase in corrosion rate of 316L with clear evidence of uniform and pitting corrosion proceeding simultaneously. Notably, the step increase in OCP for 316L steel and 254SMO during immersion in 15.3M-HAc-Br- solution indicates sudden changes in corrosion activity of the steels. The step seen for the 254SMO in 15.3M-HAc-Br- is indicative of passivation which is also supported by the XPS results, as a stable passive film was observed on the surface of alloy over the immersion time. However, the step increase in the OCP observed for 316L in 15.3MHAc-Br- is not associated with a significant decrease in corrosion rate. An alternative explanation is that the step coincides with an increase in the importance of pitting due to the evolving surface structure.From the attempts which were made to improve the corrosion resistance of the 316L stainless steel in 15.3M-HAc-Br-, both electropolishing and nitric acid passivation treatments were not sufficient to give any noticeable protection from the aggressive solution. Also, no corrosion inhibition was achieved when the three organic inhibitors, BTA, TU and 2MBI were utilised.

The master’s thesis deals with corrosion resistance of cast duplex steels. In the first part the corrosion mechanisms and their individual types are described, the second part characterizes the types of stainless steels in terms of their properties, use, structural components, and their impact on mechanical and corrosion properties of steels. Individual chapter is dedicated to duplex steels. In the experimental part the resistance of 1.4517 steel against pitting corrosion depending on the alloy contents and the PREN value was investigated. Four specimens graded according to PREN were cast. Supplemented with sample stirrer blade which was affected by corrosion during service they were subjected to corrosion test according to ASTM G48-11 standard in 6% FeCl3 solution. Cast specimens were subjected to tensile test and impact test.

An investigation into the general and pitting corrosion rates of rolled homogeneous armor (RHA) steel in immersion and saltog environments is presented. The mechanical properties of RHA steel have been studied, but the effects of corrosion on RHA have not been analyzed. An immersion environment of 3.5% NaCl was used to induce corrosion for the total testing period of 1500 hours for four immersion samples. A Qog cyclic corrosion tester was used to simulate a saltog/humidity/drying environment for four saltog samples. The different mechanisms of corrosion (general and pitting) and their associated rates were quantified through evolved hydrogen gas measurements, profilometry, Scanning Electron Microscopy (SEM) and Optical Microscopy (OM). The primary corrosion mechanism in the immersion samples was general corrosion, while the primary corrosion mechanism in the saltog samples was pitting corrosion. The immersion samples showed no signs of pitting corrosion.

No description available.

Este trabalho tem por objetivo estudar a eficiência dos oxiânions molibdato (MoO4 2-) e tungstato (WO4 2-) na inibição da corrosão localizada em aços inoxidáveis austeníticos (347 e 304L) em sistemas de água com alto grau de pureza na presença de íons cloreto (Cl-). Para avaliar a ação dos oxiânions estudados foram empregadas técnicas eletroquímicas de monitoramento do potencial de circuito aberto (Eoc), espectroscopia de impedância eletroquímica (EIS), polarização cíclica (PC) e cronoamperometria (CA). Para caracterização superficial foram utilizadas microscopia óptica (MO) e microscopia eletrônica de varredura (SEM). Os ensaios foram realizados em meios contendo somente água pura desoxigenada e água pura desoxigenada contendo íons cloreto (50, 100, 200, 300 e 500 ppm) variando a concentração (0, 10-4, 10-3 e 10-2 M) dos inibidores molibdato e tungstato de sódio. Todos os experimentos foram realizados à temperatura ambiente e em condições hidrodinâmicas controladas, empregando o sistema de eletrodo de disco rotativo (RDE) com velocidade constante de1200 rpm. Os resultados mostraram que os aços inoxidáveis 347 e 304L permanecem passivos em água pura, uma vez que o meio não é agressivo. Entretanto, a adição de íons cloreto tornou-os susceptíveis à corrosão por pites, pois os cloretos atuam como desapassivadores, fragilizando o filme passivo que fornece proteção aos aços inoxidáveis. O aumento da concentração dos íons cloreto no eletrólito aumentou a sua agressividade para os dois aços estudados, sendo observado o precoce aparecimento da corrosão. No entanto, a adição dos inibidores molibdato e tungstato de sódio melhorou a qualidade da camada passiva, aumentando os valores de potencial de pite (Ep) e de módulo de impedância, mantendo a passividade dos aços num amplo intervalo de potenciais. Ensaios cronoamperométricos mostraram que na presença dos oxiânions os valores medidos de densidade de corrente de resposta para os aços inoxidáveis 347 e 304L foram acentuadamente menores em relação aos valores obtidos na ausência dos mesmos, confirmando que os inibidores utilizados atuam na melhora da camada passiva, diminuindo a sensibilidade aos cloretos e conseqüentemente aumentando a resistência contra a corrosão por pites dos aços. O estudo mostrou que os melhores resultados para ambos os aços foram obtidos na presença de 10-2 M de inibidor, tanto para o tungstato quanto para o molibdato, sendo este com eficiência levemente melhor. Além disso, o aço 304L sem partículas incrustadas de alumina mostrou-se menos susceptível aos ataques dos cloretos do que o aço 347. Nas amostras que tiveram a superfície tratada com lixas de abrasivo de alumina, essas partículas foram incrustadas nos aços e isso levou ao desaparecimento de um potencial de pite bem definido. Na presença de alta concentração de cloretos, essas partículas foram arrancadas pelo ataque às regiões deformadas mecanicamente, localizadas ao redor das partículas incrustadas e as propriedades do aço em si puderam ser verificadas. / The aim of this work is to study the efficiency of molibdate (MoO4 2-) and tungstate (WO4 2-) oxianions in the inhibition of the localized corrosion in austenitic stainless steels (347 and 304L) in high purity water systems in the presence of chloride ions (Cl-). In order to evaluate the action of the oxianions electrochemical techniques as open circuit potential (OCP), electrochemical impedance spectroscopy (EIS), cyclic polarization (CP) and chronoamperometry (CA) were accomplished. For surface characterization optical microscopy (OM) and scanning electron microscopy (SEM) were used. The experiments were carried out in deoxygenated pure water and deoxygenated pure water containing chloride ions (50, 100, 200, 300 and 500 ppm) adding different concentrations (0, 10-4, 10-3 and 10-2 M) of molibdate and tungstate ions. All the experiments were performed at room temperature under controlled hydrodynamic conditions using a rotating disk electrode (RDE) at constant rotation speed of 1200 rpm. The results showed that 347 and 304L stainless steels remain passive in pure water, since the environment is not aggressive. However, in the presence of chloride ions they become susceptive to pitting corrosion, with chloride ions acting depassivity agents weakening the passive film that supplies protection to the stainless steels. The increase of chloride ions concentration in the electrolyte enhanced the aggressiveness for both steels evidenced by a precocious accurance of pitting corrosion. On the other hand, the addition of sodium molibdate and tungstate inhibitors improved the quality of the passive layer, increasing the pitting potentials (Ep) and the impedance modulus, improving the the passivity of steels a large of potential range. Chronoamperometric measurements showed that in the presence of oxianions response current density for 347 and 304L stainless steels was strongly diminished in relation to the values obtained in the absence of the inhibitors, confirming that the inhibitors act in the improvement of the passive layer, decreasing its sensitivity to chlorides and consequently increasing the steels resistance against pitting corrosion. Results showed that the best results for both steels were obtained in the presence of 10- 2 M tungstate or molibdate, being this latter with efficiency lightly better. Moreover, the 304L stainless steel showed to be less susceptive to pitting corrosion compared to 347 stainless steel. For stainless steel specimens previously treated with Al2O3 emery papers, Al2O3 particles become embedded in the steel surface and led to the indefinition of the pitting potential values. In the presence of high chloride concentrations, the mechanically affected region of steel in the surrounding of Al2O3 particles was attacked and Al2O3 particles were removed reveling the stainless steel own resistance to chlorides.

Nenhuma / A liga 800GN (grau nuclear) é um material utilizado na fabricação de geradores de vapor para reatores de água pressurizada (PWR) de usinas nucleares devido à sua elevada resistência à corrosão. A resistência à corrosão da liga 800GN é devida ao caráter protetor da película de óxido formada na superfície do tubo em contato com a água pressurizada à alta temperatura. No entanto, a corrosão tem sido a principal causa de falhas nos tubos dos geradores de vapor de usinas nucleares. Os problemas gerados pela corrosão têm sido atribuídos a condições e excursões da química da água do circuito secundário, muitos dos quais resultantes da entrada de água de refrigeração do condensador no circuito secundário. A experiência adquirida em diferentes centrais nucleares mostra que a composição química da água tem um papel importante na manutenção da integridade da película protetora de óxido formada na superfície do tubo. Neste trabalho foi avaliada a resistência à corrosão por pites de tubos da liga 800GN, em meio similar ao do circuito secundário de um reator PWR contendo teores de contaminação por íons cloreto de 250 ppb, 1 ppm, 5 ppm, 10 ppm e 50 ppm. A susceptibilidade dos tubos de liga 800GN ao processo de corrosão por pites foi avaliada em célula eletroquímica à temperatura de 80 C e em autoclave à temperatura de 250 oC, empregando-se a técnica eletroquímica de polarização anódica potenciodinâmica cíclica. A observação da morfologia da superfície das amostras após os ensaios eletroquímicos foi realizada por meio de microscopia ótica e microscopia eletrônica por varredura e microanálise por EDS (Energy Dispersive Spectrometry). A 80 C, a liga 800GN apresentou resistência à corrosão por pites, mesmo quando concentrações 5 ppm de Cl- foram adicionadas ao meio similar ao do ambiente secundário de um reator PWR. Corrosão por pites foi observada somente com a adição de 10 e 50 ppm de Cl-. Os ensaios eletroquímicos a 250 C mostraram que na condição normal de operação de um reator PWR e com a adição de 250 ppb de íons cloreto a liga 800GN exibiu elevada resistência à corrosão por pites, não ocorrendo nenhuma modificação na superfície do material. No entanto, ficou evidenciado que com a adição de 1 ppm de cloreto ao meio PWR iniciou-se uma modificação no filme passivo formado na superfície da liga 800GN.

The research reported in this PhD thesis provides a novel approach to estimate 3D pitting corrosion kinetics of austenitic stainless steel with exposure to chloride-containing aqueous environments. A quasi-in-situ X-ray computed tomography (X-ray CT) approach was developed, with the aim of providing an experimental methodology to estimate 3D pitting corrosion kinetics under different exposure conditions. The first part summarises a set of preliminary investigations to identify the pitting corrosion behaviour of three austenitic stainless steels (type 303 bar, type 304 plate and type 304L wire) with different inclusion contents. All observed pit densities were related to the inclusion contents, providing confidence in moving to the next stage of the project, for conducting in-situ corrosion studies using X-ray CT. The second section describes the construction of an in-situ electrochemical cell for X-ray CT studies, the aim being to provide an experimental methodology to estimate 3D pitting corrosion kinetics. Pit growth kinetics of individual pits were estimated from segmented 3D X-ray CT data. The evolution of pit current densities, associated pit stability products, and diffusivity parameters over time were obtained. The study also showed that the kinetics of multiple pits could be estimated using this novel approach, based on separating the current response of each pit over time. This was obtained by electrochemical polarisation control and measuring the total current evolution. The third section discusses the effect of plastic strain on 3D pitting corrosion kinetics. Several in-situ X-ray CT experiments were conducted, with a focus on obtaining 3D pit growth, passivation, and re-activation kinetics, to elucidate the effect of applied strain on pit stability and growth. This section explains a possible mechanism for the re-activation of pre-existing corrosion pits, showing that pits grew more rapidly during reactivation than those grown before plastic strain was applied. A marked difference in pit morphology with fractured lacy metal covers was observed with the application of strain. The implications of this observation are discussed in light of stress corrosion crack nucleation mechanisms.

The research reported in this doctoral thesis involves constructing physiochemical models that reproduce the transport behaviour of aqueous chemical species present in environments relevant to the oil and gas industry to gain an improved insight into the local electrochemistry near the electroactive surface (uniform corrosion) or inside the pit (pitting corrosion). The first part of the project involved constructing physiochemical models with one dimensional geometry with aqueous chemical species and chemical and electrochemical processes observed in oxygen (O2) containing brine environments to determine the changes in the local electrolyte composition and the potential within an initiated pit for a variety of external physical and chemical conditions. It was determined that the bottom of the pit suffers greatly from the effects of iR drop (Ohmic drop) if the pit geometry is taken to be macroscopic. The model was extended to include additional aqueous chemical species in conjunction with the chemical and electrochemical processes observed in carbon dioxide (CO2) rich environment to investigate the effects of CO2 on the local electrolyte chemistry at the bottom of the pit. It was found that the proton reduction electrochemical process on its own was incapable of supplying the high currents experimentally measured in CO2 environments via the buffering effect. The second part of the project was to investigate the influence of different experimental conditions on the polarisation behaviour of near static carbon steels in CO2 saturated brine electrolyte via multiple electrochemical measurement techniques. The key observation from this study was the presence of two distinct mass transport limited regions on the cathodic polarisation curve at natural pH (3.775). From the physiochemical model fitted to the experimental cathodic curve, the first mass transport limited region, occurring at lower cathodic potentials, was identified to be the direct reduction of carbonic acid while the second wave, occurring at slightly higher cathodic potentials, was shown to be the direct reduction of aqueous carbon dioxide. Based on the polarisation scans under forced convection, the rate of the direct reduction of carbon dioxide was determined to be under neither potential nor mass transport control. The third part of the project involved extending the existing one dimensional models to include the precipitation of salt films (iron chloride – FeCl2(s) and iron carbonate – FeCO3(s)) in O2 and CO2 saturated brine electrolyte respectively along with the capability to track their respective thickness. Furthermore, the ability of the underlying metal to undergo a change in its state from active to passive is implemented in the model via a set of rules based on the Pourbaix diagram. It was determined that the precipitation of salt films is greatly influenced by the mass transport with no or minimal thickness observed under even natural convection conditions. Furthermore the successful precipitation of salt film was determined to be a precursor step to the metal attaining passivation.

Os aÃos inoxidÃveis austenÃticos (AIAs) sÃo largamente aplicados nas indÃstrias de alimentos, transportes nuclear, petroquÃmica devido à adequada combinaÃÃo de resistÃncia mecÃnica, conformabilidade e resistÃncia à corrosÃo. Dentre estes tipos de aÃo, destaca-se o AISI 301 por sua resistÃncia mecÃnica superior. Entretanto, este tipo de aÃo apresenta um dos piores desempenhos em termos de corrosÃo. Toda a resistÃncia à corrosÃo dos AIAs se baseia em sua camada de filme passivo contendo Cr203 que pode facilmente ser destruÃda em ambientes contendo cloreto. Neste trabalho, estabeleceu-se a meta de estudar os aÃos AISI 301 LN e 316L em respeito Ãs mudanÃas na microestrutura por imposiÃÃo de deformaÃÃo e seu efeito na corrosÃo por pites, visto que o AISI 301LN foi escolhido como material base dos vagÃes que servirÃo o sistema de transporte metropolitano de Fortaleza. Empregou-se difraÃÃo de raios âX, metalografia quantitativa, microscopias Ãtica, eletrÃnica de varredura e de forÃa atÃmica para caracterizar a microestrutura, textura cristalogrÃfica, caracterizaÃÃo magnÃtica, microdureza e ensaio de imersÃo em FeCl3 6H2O para caracterizar o comportamento dos dois aÃos em corrosÃo por pites. A deformaÃÃo provocou a formaÃÃo de martensita â no aÃo 301LN e encruamento da austenita. Isto provocou o mais baixo desempenho em corrosÃo por pites. A textura cristalogrÃfica forneceu indÃcios para inferir que a transformaÃÃo austenita-ferrita se deu obedecendo a relaÃÃo de KURDJUMOV-SACHS.

No description available.