A dissertation submitted to the faculty of engineering, University of the Witwatersrand, Johannesburg in fulfillment of the requirements for the degree of master of science / Steel 3CR12 is a 12 chromium, titanium stabilized, corrosion resisting steel which was developed in South Africa in the recent past (Abbreviation abstract) / AC2017

This thesis reports a research of the corrosion mechanism and corrosion rate of steel reinforcement in concrete. Experimental results are presented to compare the corrosion behaviours of steel reinforcement in two blended-cement concretes in seawater. The experimental program included a study of the influence of crack width on macrocell corrosion, an investigation of the procedure for the determination of polarisation curves of steel in concrete and, an evaluation of the corrosion rate of steel in concrete and the influence of crack width as determined by a new polarisation curve analysis. A mechanism is proposed to interpret the different influences, in both the short and long term, of concrete crack width on the macrocell corrosion rate. This mechanism is based on the finding that the corrosion-spread phenomenon is caused by polarisation effects. An oxygen-depletion mechanism is also proposed to explain the much lower macrocell corrosion rate in the slag cement concrete than that in the flyash cement concrete. The procedure for polarisation testing of steel in concrete is found to be critical to obtaining correct polarisation curves. A twotest procedure is verified to be an appropriate procedure and used in this investigation. Experimental polarisation curves of steel in concrete are found to be very different to those expressed by the kinetic Butler-Volmer equation and, this is considered to be a result of the influence of the passive film on the steel surface in concrete. An empirical polarisation formula is developed and its interpretation is based on the postulation of two parallel kinetic processes occurring at the steel/passive-film/concrete interface; one is the active corrosion process and the other is the film growth/dissolution process. The formula is used to model experimental polarisation curves of steel in concrete through curvefitting analyses. Good curve-fitting results are obtained between the polarisation test curves and model curves. The results are used for evaluation of the corrosion rate and Tafel behaviours of steel in the two concretes and for assessment of the influence of crack width on the corrosion rate within the crack zone.

M.S. / Materials Science and Engineering / The goal of this thesis is to determine the corrosion behavior of a new class of advanced materials, namely: titanium carbide reinforced iron composites containing chromium (Fe-Cr-TiC) and chromium and manganese (Fe-Cr-Mn-TiC). TiC has excellent physical properties, such as high melting point, low density, high Vickers hardness value, high electrical resistivity and low thermal expansion. Due to their great wear resistance characteristics and toughness, these materials show potential applications in pulp and paper industries, mining and mineral processing industries, metallurgical industries, cement industries, and electric industries. Some components made of these materials may work under a combined action of corrosion and wear. This study is aimed at determining the corrosion behavior using electrochemical methods such as potentiodynamic and potentiostatic. Two different electrolytes were used in this research: 1N (0.5 M) sulfuric acid (H2SO4) and 1N (0.5 M) sodium sulfate (Na2SO4). The experiments were performed on the following materials; Fe-TiC, Fe-Cr-TiC, Fe-Cr-Mn- TiC and their matrix materials.

Aluminum-magnesium alloy (AA5083-H116) is primarily designed for marine applications such as in ship hulls and deckhouses. Its excellent combination of physical and mechanical properties makes it useful for other applications such as aircraft construction, military equipment and vehicles and automobiles.<p>This study investigated the effect of time and temperature of sensitization on the mechanical and chemical properties of AA5083-H116 such as tensile strength, yield strength and susceptibility to intergranular corrosion (IGC). Test specimens were sensitized at various temperatures (80oC, 100oC, 175oC and 200oC) for up to 672 h (4 weeks). Microhardness measurements, tensile testing, scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), inductively coupled plasma/mass spectrometry (ICP/MS) and nitric acid mass loss tests (NAMLT) were used to evaluate these effects. <p>The results obtained show that the mechanical properties of AA5083-H116 deteriorated with increasing sensitization temperature and time. The adverse effect on these properties was attributed to reduction in dislocation density and recrystallization at higher temperatures. The as-received specimens and those sensitized at 80oC showed no susceptibility to IGC. However, at higher sensitization temperatures and longer resident times, resistance to IGC decreased dramatically. The reduction in IGC resistance was attributed to precipitation of secondary phases along the grain boundaries.

Aluminum-magnesium alloy (AA5083-H116) is primarily designed for marine applications such as in ship hulls and deckhouses. Its excellent combination of physical and mechanical properties makes it useful for other applications such as aircraft construction, military equipment and vehicles and automobiles.<p>This study investigated the effect of time and temperature of sensitization on the mechanical and chemical properties of AA5083-H116 such as tensile strength, yield strength and susceptibility to intergranular corrosion (IGC). Test specimens were sensitized at various temperatures (80oC, 100oC, 175oC and 200oC) for up to 672 h (4 weeks). Microhardness measurements, tensile testing, scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), inductively coupled plasma/mass spectrometry (ICP/MS) and nitric acid mass loss tests (NAMLT) were used to evaluate these effects. <p>The results obtained show that the mechanical properties of AA5083-H116 deteriorated with increasing sensitization temperature and time. The adverse effect on these properties was attributed to reduction in dislocation density and recrystallization at higher temperatures. The as-received specimens and those sensitized at 80oC showed no susceptibility to IGC. However, at higher sensitization temperatures and longer resident times, resistance to IGC decreased dramatically. The reduction in IGC resistance was attributed to precipitation of secondary phases along the grain boundaries.

Corrosion is the most important mechanical integrity issues the petrochemical industry has to deal with. While significant research has been dedicated to studying corrosion, it is still the leading cause of pipeline failure in the oil and gas industry. Not only is it the main contributor to maintenance costs, but also it accounts for about 15-20% of releases from the petrochemical industry and 80% of pipeline leaks. Enormous costs are directed towards fixing corrosion in facilities across the globe every year. Corrosion has caused some of the worst incidents in the history of the industry and is still causing more incidents every year. This shows that the problem is still not clearly understood, and that the methods that are being used to control it are not sufficient. A number of methods to detect corrosion exist; however, each one of them has shortcomings that make them inapplicable in some conditions, or generally, not accurate enough. This work focuses on studying a new method to detect corrosion under insulation. This method needs to overcome at least some of the shortcomings shown by the commercial methods currently used. The main method considered in this project is X-ray computed tomography. The results from this work show that X-ray computed tomography is a promising technique for corrosion under insulation detection. Not only does it detect corrosion with high resolution, but it also does not require the insulation to be removed. It also detects both internal and external corrosion simultaneously. The second part of this research is focused on studying the behavior of erosion/corrosion through CFD. This would allow for determining the erosion/corrosion rate and when it would take place before it starts happening. Here, the operating conditions that led to erosion/corrosion (from the literature) are used on FLUENT to predict the flow hydrodynamic factors. The relationship between these factors and the rate of erosion/corrosion is studied. The results from this work show that along with the turbulence and wall shear stress, the dynamic pressure imposed by the flow on the walls also has a great effect on the erosion/corrosion rate.

This thesis reports a research of the corrosion mechanism and corrosion rate of steel reinforcement in concrete. Experimental results are presented to compare the corrosion behaviours of steel reinforcement in two blended-cement concretes in seawater. The experimental program included a study of the influence of crack width on macrocell corrosion, an investigation of the procedure for the determination of polarisation curves of steel in concrete and, an evaluation of the corrosion rate of steel in concrete and the influence of crack width as determined by a new polarisation curve analysis. A mechanism is proposed to interpret the different influences, in both the short and long term, of concrete crack width on the macrocell corrosion rate. This mechanism is based on the finding that the corrosion-spread phenomenon is caused by polarisation effects. An oxygen-depletion mechanism is also proposed to explain the much lower macrocell corrosion rate in the slag cement concrete than that in the flyash cement concrete. The procedure for polarisation testing of steel in concrete is found to be critical to obtaining correct polarisation curves. A twotest procedure is verified to be an appropriate procedure and used in this investigation. Experimental polarisation curves of steel in concrete are found to be very different to those expressed by the kinetic Butler-Volmer equation and, this is considered to be a result of the influence of the passive film on the steel surface in concrete. An empirical polarisation formula is developed and its interpretation is based on the postulation of two parallel kinetic processes occurring at the steel/passive-film/concrete interface; one is the active corrosion process and the other is the film growth/dissolution process. The formula is used to model experimental polarisation curves of steel in concrete through curvefitting analyses. Good curve-fitting results are obtained between the polarisation test curves and model curves. The results are used for evaluation of the corrosion rate and Tafel behaviours of steel in the two concretes and for assessment of the influence of crack width on the corrosion rate within the crack zone.

La corrosion des aciers dans le béton armé conduit à la formation de produits de corrosion (PdC) qui, outre les pertes de section, génère des contraintes mécaniques à l’interface acier/béton qui mènent, à terme, à la fissuration du béton. Le diagnostic de ce type de dégradation est souvent difficile et limite l’évaluation de l’aptitude au service de l’ouvrage, la prédiction de l’évolution des dégradations et le choix adapté d’une méthode de réparation. L’objectif de cette étude est de préciser et de quantifier les relations entre les dégradations internes dues à la corrosion de l’armature (formation de PdC et fissuration du béton) et les dégradations externes (fissuration du béton).Un programme expérimental a été défini pour appréhender ces mécanismes de dégradations. La corrosion des armatures des corps d'épreuve en béton armé confectionnés dans le cadre de cette étude a été générée de manière artificielle et accélérée en présence d'ions chlorure sous un courant imposé en considérant trois densités de courant (50,100 et 200 µA/cm²) et différentes durées.Les caractérisations électrochimiques avant et après corrosion accélérée ont permis de démontrer le passage de la corrosion passive à active des armatures dans le béton à l'échelle macroscopique. L'analyse au MEB des PdC créés à l’interface acier/béton (échelle microscopique) a montré une hétérogénéité importante de ces PdC autour de l'armature, en termes de répartition et d'épaisseurs (entre 0 et 1584 µm). Cette hétérogénéité peut s'expliquer par l'évolution des zones anodiques et cathodiques étant donné la dissymétrie géométrique des corps d’épreuve, les conditions de l'essai accéléré qui engendrent des environnements différents (gradients d'humidité, d'ions chlorure et d'oxygène) et la nature du matériau béton (granulats, porosité).La fissuration interne (orientation, ouverture et longueur de fissures) et externe (ouverture maximale de fissure) du béton d’enrobage induite par la formation des PdC a été analysée. Les faciès de fissuration internes sont constitués d’une à cinq fissures réparties en trois groupes. Les premier et second groupes rassemblent les fissures horizontales et les fissures verticales progressant des côtés de plus petit enrobage. Le troisième groupe est formé des fissures obliques situées du côté opposé aux fissures horizontales. Les ouvertures de fissures internes sont comprises entre 0,1 et 0,4 mm et leurs longueurs entre 1 et 3 cm. Les ouvertures de fissures externes maximales, localisées sur les faces du faible enrobage, varient entre 0,1 et 0,7 mm.L’effort maximum appliqué durant les essais d’arrachement diminue en fonction du taux de corrosion, mais ces taux se sont révélés trop faibles pour influencer la loi de l’interface acier/béton. Le mécanisme prépondérant de rupture observé est l’éclatement du béton d’enrobage qui est resté inchangé avec le niveau de corrosion.Un scénario de « cause à effet » entre la corrosion de l’armature et la dégradation mécanique du béton a été proposé en prenant en compte l'ensemble des résultats.A partir des nombreuses données expérimentales acquises, deux modèles ont été élaborés. Un premier modèle a été développé pour expliquer l’initiation et le développement de la corrosion des aciers. Les résultats numériques permettent de déterminer l’instant d’amorçage de la corrosion selon la densité de courant.Une deuxième modélisation qui a pour objectif d’analyser le comportement mécanique du béton armé corrodé a été mise en place. Les résultats ont montré que la seule prise en compte des épaisseurs de PdC (donnée d'entrée expérimentale) n'était pas suffisante pour obtenir un résultat numérique en adéquation avec le faciès de fissuration interne obtenu expérimentalement. Dans une seconde étape, la prise en compte de nouvelles répartitions des épaisseurs des PdC a permis d'améliorer la concordance entre les résultats numériques et expérimentaux / Corrosion of steel in reinforced concrete generates iron oxides which induce tensile stresses at the steel/concrete interface leading to the concrete cover cracking and loss of reinforcing bar cross-section. The evaluation of such pathology remains difficult and consequently limits the assessment of the structure serviceability, the knowledge on the degradation evolution, and the choice of a suitable repair method. The aim of this study is to correlate internal degradations (corrosion products formation and concrete cracking) induced by steel corrosion to external degradations (concrete cracking).The experimental program aims to determine these degradation mechanisms. The accelerated corrosion tests are carried out on reinforced concrete specimens in the presence of chloride ions by applying a constant current using three current densities (50,100 and 200 µA/cm²) during different exposure periods.Electrochemical properties of reinforced concrete specimens are determined before and after the accelerated corrosion tests. The quantitative evaluation of the corrosion products at the steel/concrete interface based on SEM observations (microscopic scale) demonstrates an important heterogeneity in the distribution and thicknesses (between 0 and 1584 µm). This heterogeneity can be explained by the evolution of anodic and cathodic zones due to different factors such as the non symmetric geometry of the specimens, the accelerated corrosion test environment (moisture, chloride ions and oxygen gradients), and the characteristics of concrete (aggregates, porosity).The internal (angular position, width, and length of cracks) and external crack patterns (maximum crack width) induced by the formation of corrosion products are analyzed. One to five internal cracks are identified in the internal crack patterns and they are classified in three groups. The first and second groups contain horizontal and vertical cracks which propagate in the direction of the shortest concrete cover. The third group is constituted of oblique cracks which are located in the opposite side of the horizontal cracks. The widths of the internal cracks range between 0.1 to 0.4 mm and their lengths between 1 to 3 cm. The maximum external crack widths are between 0.1 to 0.7 mm and are located on the shortest cover sides of the specimens.The maximum effort applied during the pull-out tests decreases with increasing levels of corrosion. However, the corrosion levels reach during the tests are too low to affect the steel/concrete interface behavior. The failure mode identified during the testing is concrete splitting failure regardless the corrosion level. A cause/effect scenario is proposed between steel corrosion and the mechanical induced degradation considering all experimental results.Based on experimental results, two models are proposed. The first one is developed to explain corrosion initiation and propagation. This model is able to determine the corrosion initiation time for each current density.The second model analyses the concrete cover mechanical behavior. The numerical results show that taking into account only the thickness of corrosion products (as an experimental input) does not generate a numerical cracking pattern similar to the experimental one. Then, complementary calculations considering a different distribution of the corrosion product’s thicknesses allow enhancing the agreement between experimental and numerical results

In this work, copper bimetallic corrosion and inhibition in ultra large scale interconnect fabrication process is explored. Corrosion behavior of physical vapor deposited (PVD) copper on ruthenium on acidic and alkaline solutions was investigated with and without organic inhibitors. Bimetallic corrosion screening experiments were carried out to determine the corrosion rate. Potentiodynamic polarization experiments yielded information on the galvanic couples and also corrosion rates. XPS and FTIR surface analysis gave important information pertaining inhibition mechanism of organic inhibitors. Interestingly copper in contact with ruthenium in cleaning solution led to increased corrosion rate compared to copper in contact with tantalum. On the other hand when cobalt was in contact with copper, cobalt corroded and copper did not. We ascribe this phenomenon to the difference in the standard reduction potentials of the two metals in contact and in such a case a less noble metal will be corroded. The effects of plasma etch gases such as CF4, CF4+O2, C4F8, CH2F2 and SF6 on copper bimetallic corrosion was investigated too in alkaline solution. It was revealed that the type of etching gas plasma chemistry used in Cu interconnect manufacturing process creates copper surface modification which affects corrosion behavior in alkaline solution. The learning from copper bimetallic corrosion studies will be useful in the development of etch and clean formulations that will results in minimum defects and therefore increase the yield and reliability of copper interconnects.

Cette thèse a porté sur la conception d'un capteur de corrosion passif, sans contact de moyenne portée. Les solutions existantes sans fil concernent soit des capteurs à architecture classique, soit des solutions passives. Dans le premier cas, le capteur de corrosion est actif et peut être interrogé à longue portée. Dans le second cas, les solutions passives existantes ne fonctionnent qu’avec des distances de lecture de quelques centimètres du fait des basses fréquences utilisées. L’objectif de ce travail était de répondre à ce besoin. Pour cela, nous nous sommes inspirés de la technologie RFID (Radio Frequency Identification) passive chipless pour le développement d’un capteur basé sur une fonction hyperfréquence. La première structure réalisée a été une ligne microruban, dont le ruban est constitué d’une couche mince d’un élément sensible à la corrosion. Dans ce cas, la corrosion de la ligne s’est traduite par une variation d’amplitude du fait de l’apparition de pertes expliquées principalement par l’effet de peau ou la création de défauts. Une deuxième structure hyperfréquence a été élaborée en se basant sur un stub (circuit ouvert) qui a permis de suivre le processus de la corrosion via une variation de fréquence. Comme le cas de la ligne microruban, cette structure nous a permis de distinguer la corrosion uniforme et la corrosion localisée. Grâce à la mise en évidence de ces fonctionnalités, diverses stratégies de contrôle de la corrosion peuvent être imaginées et un démonstrateur a été réalisé. Le point clé du démonstrateur proposé est une augmentation de la distance de lecture dans la technologie RFID chipless, ceci a été rendu possible en considérant l’isolation Tx / Rx du lecteur. Dans ce contexte, trois types d’antennes ont été étudiées. Afin d’augmenter encore la distance de lecture, d’autres techniques d’isolation ont été proposées : l’utilisation d’un déphaseur mais aussi l’isolation temporelle par l’utilisation d’une ligne à retard SAW. Grâce à ces 2 méthodes, une distance de lecture de deux mètres a été obtenue. Suite aux caractérisations RF des métaux soumis à la corrosion discutées, nous avons aussi élaboré une sonde RF à champ proche permettant de diagnostiquer la corrosion de surfaces métalliques. / This thesis focused on the design of a passive wireless corrosion sensor. Existing wireless solutions concern either classic architecture sensors or passive solutions. In the first case, the corrosion sensor is active and can be interrogated at long range. In the second case, the existing passive solutions only work with reading distances of a few centimeters because of the low frequencies. The objective of this study was to respond to this need. That’s why; we were inspired by the RFID( Radio Frequency Identification) passive chipless technology for the development of a sensor based on a microwave function. The first structure was a microstrip line, of which the strip is composed of a thin layer of an element sensitive to corrosion. In this case, the corrosion of the line is proven by an amplitude variation due to losses principally explained by the skin effect or the creation of defects. A second microwave structure was developed based on a stub (open circuit) which allowed us to follow the process of corrosion via a frequency variation. Much like the microstrip line, this structure allowed us to distinguish between uniform corrosion and localised corrosion. Due to the highlighting of these features, different corrosion control strategies can be imagined and a demonstrator was executed. The key point of the proposed demonstrator is an increase in the reading distance in the chipless RFID technology; this was made possible by taking into consideration the isolation TX / Rx of the reader. In this context, three types of antennas were studied. In order to increase the reading distance, other isolation techniques were proposed: the use of a phase shifter but also a temporal isolation using a SAW delay line. Thanks to these two methods, a reading distance of two meters was obtained. Following the RF characterizations of metals exposed to the discussed corrosion, we also developed a near field RF probe, which allows corrosion diagnostic of metal surfaces.