Pitting corrosion is one of the most destructive types of metal loss. The purpose of this study was to investigate the evolution, or in other words, the propagation, of a single pit in carbon steel after the initiation stage. In view of the chemical and electrochemical reactions inside a single pit in carbon steel, a two dimensional model that allows the prediction of pit evolution was developed. Eleven species in aqueous sodium chloride solution and two neutral complexes were considered in the model. Given that the active-passive transition of a metal is a key phenomenon in pitting, the equations used to construct a Pourbaix diagram for iron were incorporated in the model as rules to govern passivation behaviour. By using the finite element package COMSOL Multiphysics as a tool, the Nernst-Planck equations for the mass transport and potential variations were solved. In addition, the multiphysics model was extended with Moving Boundary (ALE) mode to predict shapes of pits. The results of the study were that the model was able to investigate migration of ionic species, account for the active-passive transition of metal and also able to show the effect of solid precipitation. The model was able to show movement of the boundaries of a pit and hence, predict the shapes of pit at a given range of time. The results were discussed in comparison to the Pourbaix diagram of iron and compared with the experimental results and published models reported in literature. The principal conclusion is that modelling corrosion activities with integrated thermodynamic equations based on Pourbaix diagram methods is an outstanding way to model any other corrosion activities.

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.

La détérioration des infrastructures au Canada due à la corrosion des armatures est l'un des défis majeurs de l'industrie de la construction. Les progrès récents dans la technologie des polymères ont conduit au développement d'une nouvelle génération de barres d'armature à base de fibres renforcées de polymères (PRF), (en particulier les fibres de verre). Ces barres, résistant à la corrosion, ont montré un grand potentiel d'utilisation pour mieux protéger les infrastructures en béton armé contre les effets dévastateurs de la corrosion. Avec la publication du nouveau code S807-10 "Spécifications pour les polymères renforcés de fibres" et la production de barres en PRF de très haute qualité, celles-ci représentent une alternative réaliste et rentable par rapport à l'armature en acier pour les structures en béton soumises à de sévères conditions environnementales. La conception des éléments en béton armé de barres en PRF est généralement gouvernée par l'état de service plutôt que l'état ultime. Par conséquent, il est nécessaire d'analyser les performances en flexion et le comportement en service en termes de déflexion et de largeur de fissures des éléments en PRF sous charges de service et de vérifier que ces éléments rencontrent les limites des codes. Aussi, de récents développements dans l'industrie des PRF ont conduit à l'introduction des barres en PRF avec des configurations de surface et des propriétés mécaniques différentes. Ces développements sont susceptibles d'affecter leur performance d'adhérence et, par conséquent, la largeur des fissures dans les éléments en PRF. Cependant, les codes de conception et les guidelines de calcul fournissent une valeur unique pour le coefficient d'adhérence (k[indice inférieur b]) en tenant compte des configurations de surface et en négligeant le type de barre en PRF, le diamètre de la barre, et le type de béton et de sa résistance. En outre, le code canadien S807-10 "Spécifications pour les polymères renforcés de fibres" fournit une étape en classant les barres en PRF par rapport à leur module d'élasticité (E[indices inférieurs frp]). Ces classifications ont été divisées en trois classes : Classe I (E[indices inférieurs frp]<50 GPa), Classe II (50 GPa [plus petit ou égal] E[indices inférieurs frp]< 60 GPa) et Classe III (E[indices inférieurs frp] [plus grand ou égal] 60 GPa). Ce programme de recherche vise à étudier expérimentalement le comportement en flexion des éléments en béton en service armé avec différents paramètres sous charges statiques. Le programme expérimental est basé sous plusieurs paramètres, dont les différents ratios de renforcement, différents types de barres (différentes classes comme classifiées par le CAN/CSA S807-10), le diamètre et la surface de la barre, la configuration ainsi que la résistance du béton. De plus, les recommandations actuelles de design pour les valeurs de k[indice inférieur b] et la vérification de la dépendance des valeurs de k[indice inférieur b] sur le type de barres (verre ou carbone), le diamètre des barres et le type de béton et sa résistance ont été étudiées. Le programme expérimental comprenait la fabrication et les essais sur 33 poutres à grande échelle, simplement appuyées et mesurant 4250 mm de long, 200 mm de large et 400 mm de hauteur. Vingt et sept poutres en béton ont été renforcées avec des barres en PRF à base de verre, quatre poutres en béton ont été renforcées avec des barres de PRF à base de carbone, et deux poutres ont été renforcées avec des barres en acier. Toutes les poutres ont été testées en flexion quatre points sur une portée libre de 3750 mm. Les paramètres d'essai étaient: le type de renforcement, le pourcentage d'armature, le diamètre des barres, configurations de surface et la résistance du béton. Les résultats de ces essais ont été présentés et discutés en termes de résistance du béton, de déflection, de la largeur des fissures, de déformations dans le béton et l'armature, de résistance en flexion et de mode de rupture. Dans les trois articles présentés dans cette thèse, le comportement en flexion et la performance des poutres renforcées de barres en PRFV et fabriquées avec un béton normal et un béton à haute performance ont été investigués, ainsi que les différentes classes de barres en PRFV et leurs configurations de surface. Les conclusions des investigations expérimentales et analytiques contribuent à l'évaluation des équations de prédiction de la déflection et des largeurs de fissures dans les codes de béton armé de PRF, pour prédire l'état de service des éléments en béton renforcés de PRF (déflection et largeur de fissures). En outre, à la lumière des résultats expérimentaux de cette étude, les équations de service (déflection et largeur des fissures) incorporées dans les codes et guidelines de design [ACI 440.1R-06, 2006; ISIS Manual No.3, 2007; CAN/CSA-S6.1S1, 2010; CAN/CSA-S806, 2012] ont été optimisées. En outre, les largeurs de fissures mesurées et les déformations ont été utilisées pour évaluer les valeurs courantes de k[indice inférieur b] fournies par les codes et les guidelines de calcul des PRF. En outre, les conclusions ne prennent pas en charge la valeur unique de k[indice inférieur b] pour les barres en PRF de types différents (carbone et verre) avec des configurations de surface similaires et s'est avéré être dépendant du diamètre de la barre.

In this research, corrosion behaviour of A36 carbon steel under engineered disbonded coating was investigated in sulphuric acid solutions containing sodium chloride and iron (III) sulphate. Scanning electron microscopy (SEM) and x-ray diffraction (XRD) analyses were carried out to study the morphology and phase composition of corrosion products formed on the carbon steel surface. The results of the SEM analysis showed that only general and pitting corrosion occurred on the carbon steel surface with the engineered crevice. The size of the pits increased as the sulphuric acid and sodium chloride concentrations increased. Moreover, the corrosion products had an open, irregular and loose structure at the pits mouth. The loose and open structure of the corrosion products facilitates diffusion of chloride ions, oxygen, water and contaminants into the carbon steel surface. In contrast, the corrosion products had a very compact and continuous structure outside the pits which provided a good protection against further corrosion. The x-ray diffraction analysis showed that the corrosion products layer mainly consisted of lepidocrocite (γ-FeOOH), goethite (α-FeOOH) and iron sulphide (FeS) on the crevice edges. The Pourbaix diagram of iron in sulphuric acid solution at room temperature indicates that iron sulphide is formed on the metal surface at different pH values. The akaganeite (β-FeOOH) diffraction peak was not identified in any spectrum which could be due to the low concentration of chloride ions in the solutions. Furthermore, the number of lepidocrocite peaks decreased as the sulphuric acid concentration increased from 10 g l-1 to 50 g l-1. The lepidocrocite is dissolved in the presence of sulphuric acid, and the dissolved ion acts as an oxidant to the metal and hence lower lepidocrocite peaks are identified. Electrochemical noise measurement (ECN) testing was also performed to investigate the corrosion process occurring on the carbon steel surface with the engineered crevice. The results of the ECN measurements showed that current increased during first few minutes and then decreased slightly. Also, the coupled potential did not change after an initial shift in negative direction. The low current flowing through the carbon steel electrodes and the constant potential showed that the crevice corrosion did not develop. These results imply that the crevice corrosion may not occur on the carbon steel surface in acidic solutions containing chloride ions.

It is well-known that concrete permeability is a good indicator of its expected durability until it remains uncracked. However, in various stages of its service life, different types of cracking in concrete can be developed due to exposure to different deterioration processes such as early plastic shrinkage or chloride-induced reinforcement corrosion. Although these cracks may not endanger concrete’s structural performance from the mechanical point of view, they create a pathway for aggressive ions that can initiate degradation processes, lead to increase in concrete permeability and thus reduce its durability. Cracking in concrete might not be preventable, but its capability to naturally seal small cracks, named autogenous self-healing (SH), provides an additional feature to manufacture more durable concrete structures. However, natural self-healing capability of concrete is limited and therefore it is typically omitted in the design of concrete structures. Hence, more attention has been recently paid to Engineered Self-healing Concrete (EShC) which is associated with artificially triggered healing mechanisms into the cementitious matrix by incorporating various substances such as crystalline products. EShC helps in reducing concrete permeability; thus, increasing its service-life and durability. Due to formation of needle-shaped pore-blocking crystals, Crystalline Admixtures (CA), as a candidate from the Permeability-Reducing Admixtures (PRA) category, can be implemented into concrete mixtures to fabricate EShC concretes. Crystalline waterproofing technology is not new, but still is unknown to many researchers, engineers, and construction industry professionals. The lack of knowledge of its microstructure and self-healing properties limits CA’s proper usage in the construction industry. The techniques to assess the self-healing capability of mortar and concrete are not well-standardized yet. No research work has been done to address certain durability characteristics of this material (i.e. electrical resistivity (ER) or chloride diffusivity) especially when combined with Supplementary Cementitious Materials (SCM) and Portland Limestone Cement (PLC). Since the resistance of concrete against ions’ penetration is a function of its permeability, it might be a straightforward and reliable parameter to rapidly evaluate concrete’s durability during its intended service life. Hence, electrical resistivity measurement is considered as an indirect and alternative tool for other time-consuming permeability testing techniques to examine the CA’s efficiency as it modifies the concrete’s microstructure by crystals’ deposition; thus, leads to permeability improvement. In comparison to previous studies, on a larger scale, this thesis aims to systematically study the effects of CA on the microstructural features, self-healing properties and long-term durability and resistivity of cement-based materials and in addition, draw some comprehensive conclusions on the use of CA in new and repair applications. This study is divided into three major phases to propose all-inclusive work on using CA in construction industry. To satisfy the goals of each individual phase, a test matrix consisting of a series of four mixes with variables such as use of PLC or presence of CA in powder form is considered. In order to address to the lack of research and industry knowledge discussed above, this PhD thesis includes the following phases: Phase (I) In this phase, the main focus is on the microstructural properties and the changes in the pore structure and chemical compositions of the cement phase of mortar mixes when treated with CA. These microstructural features are studied using Scanning Electron Microscope (SEM) and Scanning Transmission Electron Holography Microscope (STEHM). Moreover, physical and chemical characteristics of the hydration products are determined using image analysis and Energy Dispersive X-ray (EDX) Spectroscopy, respectively. Phase (II) This phase is allocated to macro-level investigation of durability characteristics such as chloride/water permeability and electrical resistivity of concrete structures containing CA and PLC cement. To non-destructively measure the chloride ion concentration in the field conditions, both changes in corrosion potential of rebars and concrete electrical resistivity in treated circular hollow-section steel reinforced columns exposed to simulated marine environment is monitored and compared over a 2-year period with control samples. In addition, laboratory-size concrete samples are studied to investigate the effects of CA presence on long-term resistivity, rapid chloride permeability, water permeability and chloride diffusivity of concrete. Later, a resistivity-based model is developed to predict long-term performance of concretes incorporating slag or metakaolin, studied in various environmental conditions. The long-term goal of this phase is to develop a standard design guideline and durability-based model. Phase (III) Using an innovative self-healing testing method [1], quantitative analysis of crack closure ability and self-healing potential of CA treated and control concretes with OPC or PLC cement is accomplished during this phase. The obtained results from first phase showed that hydrated CA particle revealed fine, compact, homogenous morphology examined by STEHM and its diffraction pattern after water-activation indicated nearly amorphous structure, however, diffuse rings, an evidence for short-range structural order and sub-crystalline region, were observed which requires further investigation. The SEM micrographs taken from specimen’s fractured surface showed formation of pore-blocking crystals for all treated mixes while similar spots in un-treated sections were left uncovered. Although needle-shaped crystals were observed in the treated mortar specimens, but not all of them had shapes and chemical compositions other than ettringite (well-known to form needle-like crystals). Using backscatter SEM images and EDX spectrums, examination of polished mortar sections with and without CA also showed typical hydration phases, forming in the control system. Results from phase II showed that concretes treated with CA had almost 50% lower water penetration depth and thus smaller permeability coefficient when compared with the virgin OPC or PLC concretes. According to salt ponding test results, the use of CA helped in enhancing the resistance to chloride penetration compared to control concrete. This improvement increases with increasing in concrete age. Strong linear relationship between Surface Resistivity (SR) and Bulk Resistivity (BR) data was observed which indicates that these test methods can be used interchangeably. The presence of SCM in concrete indicated considerable increase in both SR and BR compared to control concrete. Concretes incorporating slag or metakaolin have tendency to react more slowly (or rapidly in MK case), consume calcium hydroxide over time, form more Calcium Silicate Hydrate (C-S-H) gel, densify internal matrix, and also reduce OH- in the pores’ solution; thus, increase concrete electrical resistivity. For laboratory specimens, environmental conditions such as temperature variation and degree of water saturation indicated considerable effects on electrical resistivity measurements. As temperature or water content of concrete decreases, its electrical resistivity greatly increases by more than 2-3 times from reference environmental condition. This is mostly because of variation or accessibility in electron mobility. Experimental results from field investigation showed that electrical resistivity readings were highly influenced by the presence of rebar and concrete moisture conditions. In addition, concrete cover thickness and CA addition into cementitious matrix had a negligible effect on its resistivity. In the last phase, an optical microscope was used to measure the average crack width. OPC samples had an average measured crack width of 0.244 mm as compared to 0.245 mm for OPC-CA, 0.251 mm for PLC, and 0.247 mm for PLC-CA. Self-healing test results also showed 90% self-healing ratio for CA modified mix within few days after starting experiment. Addition of CA into the mix led to higher rates of healing and full crack closure (width up to 250 µm) when compared to reference concrete. An empirical equation that relates water initial flow rate to the crack width (Q∝〖CW〗^3) was also proposed in this phase. Presence of PLC and CA in the mixture resulted in positive improvement in crack-closing capability and self-healing ratio. / Graduate / 2019-09-11

Sacrificial metallic coatings have been used in the past, for protecting steel in industrial and urban developments. It has been suggested that thermally sprayed aluminium coatings, immersed in marine environments, are also capable of protecting steel by providing galvanic protection. Researchers have also speculated that the growth of inert oxide products, on top of the coating as well as inside pores and cracks, could enhance even further its protective “shielding” properties. In addition, the self-healing abilities of the coatings, in case of mechanically induce damage, are still a matter of debate. This research project takes a critical look at these assumptions, focusing on the electrochemical response of aluminium metal sprayed (AMS) coatings immersed in 0.6 M NaCl and 0.6 M Na2SO4 solutions, in order to investigate how the presence of chlorides can alter the corrosion behaviour of these coatings. For such, a thin aluminium protective coating was deposited over two different panels (aluminium 1050 and low carbon steel), by the steel making company Fairfield-Mabey, using electric arc thermal spraying (TS). Subsequently, the coated panels were sectioned into smaller specimens, and with the aid of a SEM/EDS, and XRD, observations and analysis were conducted in their surfaces and cross sections, in order to determine the morphology, quality of deposition, and chemical composition of the coatings. Internal porosity/oxide growth after immersion, was studied using 3-D X-ray tomography scanning. Furthermore, the electrochemical behaviour of the coatings (intact and scribed) was also investigated, initially by analyzing the evolution of the open circuit potential in time, when immersed in chloride rich and chloride free environments. Additionally, the anodic polarization behaviour of the substrate and coatings were simultaneously analyzed, by connecting a zero resistance ammeter (ZRA) with the W.E. terminal of a potentiostat. To conclude, EIS and Rp vs. time plots were made in order to corroborate the data obtained from other tests. Results show that although the coating can generate superficial and internal corrosion products, these oxides are not isolating in nature nor will enhance its protective properties. On the other hand, the corrosion potential behaviour of the coatings revealed that AMS coatings have a more active than the substrate; regardless of the environment in which they were immersed or their substrate. Nevertheless, it was also observed that AMS coatings deposited onto steel will corrode faster than their substrates, and for that matter capable of offering corrosion protection, exclusively if chlorides are present in the solution.

The transportation infrastructure in the United States is a complex system that is vital to the everyday operations of the country. Bridges are a significant asset of this network, with many of them approaching the end of their service life. Corrosion is a common cause of deterioration which ultimately results to structural deficiency for the aging bridges. The deterioration rate is a multi-aspect factor that makes bridge inspections crucial. However, the current bridge inspections are very costly and potentially unsafe for the involved personnel. To lower costs and increase safety, many state DOT’s and universities have decided to perform research on Unmanned Aerial Vehicles (UAVs), or drones. This thesis explores the implementation of drone technology in bridge inspections and investigates their limits for corrosion detection and estimation. The first part of this thesis summarizes the responses obtained from a questionnaire sent to the personnel from the Massachusetts Department of Transportation (MassDOT). The second and third parts of this thesis summarizes how states have utilized UAVs for bridge inspections, including the selected drones and the attached equipment. The last part presents technologies that can be used to detect and measure corrosion, and how they can be used in conjunction with drones to quantify section loss of steel beams.

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Orientador: Maria Clara Filippini Ierardi / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-05T03:30:54Z (GMT). No. of bitstreams: 1 Nascimento_AlexMaiado_M.pdf: 9829466 bytes, checksum: 78b8c487039e438993230c1c4d52544c (MD5) Previous issue date: 2005 / Resumo: Neste trabalho procurou-se observar as mudanças microestruturais e os efeitos na resistência à corrosão dos aços inoxidáveis duplex UNS S32304 e S32205, bastante utilizados pela indústria petrolífera, após realização de tratamentos superficiais por refusão a laser. Foram realizados inicialmente vários testes para a determinação experimental dos parâmetros de processo. Após a escolha otimizada dos parâmetros, as mudanças microestruturais foram analisadas por microscopia ótica, microscopia eletrônica de varredura - MEV, difração de raios- X e microdureza Vickers. Com isso, obteve-se dados que puderam ser comparados a condição inicial das ligas. Para analisar o comportamento corrosivo das ligas, antes e após os tratamentos, foram feitos ensaios de polarização cíclica com utilização da solução de 3,5% de NaCI (água do mar artificial), já que os aços inoxidáveis duplex estão sendo bastante utilizados em situações offshore na indústria do petróleo. Os resultados obtidos mostraram que quando tratadas superficialmente a laser, devido à rápida resolidificação, as ligas praticamente ferritizaram, e como o teor de nitrogênio existente na composição de ambas ligas é superior ao seu limite de solubilidade na ferrita, ocorreu uma precipitação de Cr2N(nitretos de cromo) na matriz ferrítica o que promoveu uma perda de resistência à corrosão, porém um aumento significativo de dureza superficial / Abstract: The objective of this work is to observe the micros1ructural changes and effects on corrosion resistance of the duplex stainless steels UNS S32304 and S32205, commonly used by the petroleum industry, following the execution of laser surface remelting treatments. Various initial tests were carried out to determine the parameters for the experimental process. Following the optimum choice of parameters, microstructural changes were analyzed by means of optical microscopy, Scanning Electron Microscopy, X-ray Diffraction and Vickers Microhardness. In this way, data was obtained, which could then be compared with the starting condition of the alloys. In order to analyze the corrosive behavior of the alloys before and after the treatments, cyclic polarization tests were carried out. A solution of 3.5% NaCI (artificial sea water) was utilized, as duplex stainless steels are regularly used by the petroleum industry in offshore locations. The results obtained showed that when treated superflcially by laser, due to rapid resolidification, the alloys became almost ferritic, and since the leveI of nitrogen in the composition of both alloys is superior to their solubility limit in ferrite, a precipitation of Cr2N (chromium nitrides) occurred in the ferritic matrix, causing loss of corrosion resistance, thus signifying an increase in surface hardness / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica