abstract: Dissimilar metal joints such as aluminum-steel joints are extensively used in automobile, naval and aerospace applications and these are subjected to corrosive environmental and mechanical loading resulting in eventual failure of the structural joints. In the case of aluminum alloys under aggressive environment, the damage accumulation is predominantly due to corrosion and is accelerated in presence of other metals. During recent years several approaches have been employed to develop models to assess the metal removal rate in the case of galvanic corrosion. Some of these models are based on empirical methods such as regression analysis while others are based on quantification of the ongoing electrochemical processes. Here, a numerical model for solving the Nernst- Planck equation, which captures the electrochemical process, is implemented to predict the galvanic current distribution and, hence, the corrosion rate of a galvanic couple. An experimentally validated numerical model for an AE44 (Magnesium alloy) and mild steel galvanic couple, available in the literature, is extended to simulate the mechano- electrochemical process in order to study the effect of mechanical loading on the galvanic current density distribution and corrosion rate in AE44-mild steel galvanic couple through a multiphysics field coupling technique in COMSOL Multiphysics®. The model is capable of tracking moving boundariesy of the corroding constituent of the couple by employing Arbitrary Langrangian Eulerian (ALE) method.Results show that, when an anode is under a purely elastic deformation, there is no apparent effect of mechanical loading on the electrochemical galvanic process. However, when the applied tensile load is sufficient to cause a plastic deformation, the local galvanic corrosion activity at the vicinity of the interface is increased remarkably. The effect of other factors, such as electrode area ratios, electrical conductivity of the electrolyte and depth of the electrolyte, are studied. It is observed that the conductivity of the electrolyte significantly influences the surface profile of the anode, especially near the junction. Although variations in electrolyte depth for a given galvanic couple noticeably affect the overall corrosion, the change in the localized corrosion rate at the interface is minimal. Finally, we use the model to predict the current density distribution, rate of corrosion and depth profile of aluminum alloy 7075-stainless steel 316 galvanic joints, which are extensively used in maritime structures. / Dissertation/Thesis / Masters Thesis Mechanical Engineering 2015

La « shadow corrosion » est un phénomène observé sur les gaines en alliages de zirconium des assemblages de combustibles dans les réacteurs nucléaires. Il consiste en l'augmentation de la corrosion sur les zones de la gaine qui sont à proximité d'autres parties de l'assemblage en Inconel. Afin d'améliorer la compréhension de ses mécanismes, des modèles numériques sont développés suivant deux axes d'études. Un premier modèle de couplage galvanique a pour but de dégager les facteurs de premier ordre. Les résultats des simulations montrent que l'intensité du courant anodique, et sa dépendance en potentiel, contrôlent le caractère local (effet d'ombre) de ce phénomène. D'autre part, cet effet nécessitant un courant cathodique assez élevé révèle l'importance du pouvoir oxydant de l'électrolyte. Un deuxième modèle d'oxydation du zirconium est développé en intégrant le transport multi particules dans l'oxyde. Ce modèle, couplé aux effets d'interfaces (métal/oxyde et oxyde/électrolyte), permet de démontrer le rôle crucial de la polarisation et de l'hydrogène provenant de la dissociation de l'eau sur les cinétiques d'oxydation. A partir de ces modèles, un scénario explicatif de la shadow corrosion est élaboré suggérant l'importance de la radiolyse de l'eau. / La « shadow corrosion » est un phénomène observé sur les gaines en alliages de zirconium des assemblages de combustibles dans les réacteurs nucléaires. Il consiste en l'augmentation de la corrosion sur les zones de la gaine qui sont à proximité d'autres parties de l'assemblage en Inconel. Afin d'améliorer la compréhension de ses mécanismes, des modèles numériques sont développés suivant deux axes d'études. Un premier modèle de couplage galvanique a pour but de dégager les facteurs de premier ordre. Les résultats des simulations montrent que l'intensité du courant anodique, et sa dépendance en potentiel, contrôlent le caractère local (effet d'ombre) de ce phénomène. D'autre part, cet effet nécessitant un courant cathodique assez élevé révèle l'importance du pouvoir oxydant de l'électrolyte. Un deuxième modèle d'oxydation du zirconium est développé en intégrant le transport multi particules dans l'oxyde. Ce modèle, couplé aux effets d'interfaces (métal/oxyde et oxyde/électrolyte), permet de démontrer le rôle crucial de la polarisation et de l'hydrogène provenant de la dissociation de l'eau sur les cinétiques d'oxydation. A partir de ces modèles, un scénario explicatif de la shadow corrosion est élaboré suggérant l'importance de la radiolyse de l'eau.

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Corrosion of drinking water distribution systems can cost water utilities and homeowners tens of billions of dollars each year in infrastructure damage, adversely impacting public health and causing water loss through leaks. Often, seemingly innocuous choices made by utilities, plumbers, and consumers can have a dramatic impacts on corrosion and pipeline longevity. This work demonstrated that brass pipe connectors used in partial lead service line replacements (PLSLR) can significantly influence galvanic corrosion between lead and copper pipes. Galvanic crevice corrosion was implicated in a fourfold increase in lead compared to a traditional direct connection, which was previously assumed to be a worst-case connection method. In field sampling conducted in two cities, a new sampling method designed to detect particulate lead risks demonstrated that the choice of flow rate has a substantial impact on lead-in-water hazards. On average, lead concentrations detected in water at high flow without stagnation were at least 3X-4X higher than in traditional regulatory samples with stagnation, demonstrating a new 'worst case' lead release scenario due to detachment of lead particulates. Although galvanized steel was previously considered a minor lead source, it can contain up to 2% lead on the surface, and elevated lead-in-water samples from several cities were traced to galvanized pipe, including the home of a child with elevated blood lead. Furthermore, if both galvanized and copper pipe are present, as occurs in large buildings, deposition corrosion is possible, leading to both increased lead exposure and pipe failures in as little as two years. Systematic laboratory studies of deposition corrosion identified key factors that increase or decrease its likelihood; soluble copper concentration and flow pattern were identified as controlling factors. Because of the high copper concentrations and continuous flow associated with mixed-metal hot water recirculating systems, these systems were identified as a worst-case scenario for galvanic corrosion. Deposition corrosion was also confirmed as a contributing mechanism to increased lead release, if copper pipe is placed before a lead pipe as occurs in partial service line replacements. Dump-and-fill tests confirmed copper solubility as a key factor in deposition corrosion impacts, and a detailed analysis of lead pipes from both laboratory studies and field tests was consistent with pure metallic copper deposits on the pipe surface, especially near the galvanic junction with copper. Finally, preliminary experiments were conducted to determine whether nanoparticles from novel water treatment techniques could have a negative impact on downstream drinking water pipeline infrastructure. Although increases in the corrosion of iron, copper, and stainless steel pipes in the presence of silver and carbon nanomaterials were generally small or non-existent, in one case the presence of silver nanoparticles increased iron release from stainless steel by more than 30X via a localized corrosion mechanism, with pitting rates as high as 1.2 mm/y, implying serious corrosion consequences are possible for stainless steel pipes if nanoparticles are present. / Ph. D.

In many source waters across the United States (US), chloride levels are increasing and this change could be problematic for galvanized iron pipe (GIP) installed in consumers' homes and buildings. The higher levels of chloride might increase the rate of galvanic corrosion between the sacrificial zinc coating and the underlying iron (steel) pipe. There are also concerns that the iron in GIP can accumulate lead on its surface from upstream lead service lines, occasionally causing high lead in water from GIP during scale sloughing and associated red water events. The role of high chloride and potential mitigation strategies by orthophosphate and alkalinity on galvanic iron-zinc corrosion in GIP were examined by using new iron and zinc wires, and complementary studies with 85-year-old harvested GIP coupons from the Washington Suburban Sanitary Commission (WSSC). Sequential samplings on a constructed pilot-scale test rig with copper – lead – GIP ¬– brass meter configuration were used to evaluate lead source fingerprinting methods (metal co-occurrence, correlating the plumbing configuration to sample profiling data, and evaluation of lead isotope ratios) and role of flow rate. As chloride concentration increased from 2.6 to 554 mg/L, galvanic current and weight loss of sacrificial zinc increased by about an order of magnitude. Iron leaching also increased by 4.4 times as chloride levels increased by a factor of 12 in WSSC modified water to simulate actual road salt runoff events. Increased orthophosphate or alkalinity could at least partly counter the adverse effects of chloride, as the average iron concentration decreased by 43% as orthophosphate level increased from 3.8 to 11.2 mg/L as P, and average iron concentrations decreased by 32% as alkalinity increased from 50 to 90 mg/L as CaCO3. Applying fingerprinting methods on sequential samples has the potential to determine whether premise plumbing contains GIP and/or lead pipe. Specifically, the metal co-occurrence fingerprinting technique was successful in identifying the location of GIP by the detection of low-level cadmium, and the lead isotope ratio fingerprinting technique was fairly successful in identifying lead pipe. Additionally, our study found that GIP was not contaminated by an upstream lead pipe after five months of conditioning; hence, water discoloration (iron level > 400 ppb) does not always indicate lead problems from GIP. However, with longer exposure of GIP to lead pipe, the magnitude of the problem might increase. As flow rate increased from 0.9 to 2.4 GPM, the median particulate iron release increased by 3.3 times, and the median particulate lead release (>83% particulate lead) increased by 4.9 times. / Master of Science / In many source waters across the United States (US), chloride levels are increasing and this change could be problematic for galvanized iron pipe (GIP) installed in consumers' homes and buildings. The higher levels of chloride might increase the rate of galvanic corrosion in GIP. There are also concerns that the iron in GIP can accumulate lead on its surface from upstream lead service lines, occasionally causing high lead in water from GIP during scale sloughing and associated red water events. The role of high chloride and potential mitigation strategies for GIP by adjusting orthophosphate and alkalinity were examined by conducting bench scale testing. Sequential samplings on a constructed pilot-scale test rig with different lead source pipe sections were used to evaluate lead source fingerprinting methods and role of flow rate. Higher chloride in water increased galvanic current and weight loss of zinc coating as chloride concentration increased from 2.6 to 554 mg/L in the fundamental experiments. Iron leaching also increased as chloride levels increased in the GIP coupon testing. Increasing orthophosphate or alkalinity proved to counter the adverse effects of chloride as the average iron concentration decreased. Sampling profiles can be useful in determining whether premise plumbing contains GIP or lead pipe by using fingerprinting methods. Iron and lead leaching from GIP increased as the water flow rate increased.

With the reliability requirements of automobile microelectronics pushing towards near 0 ppb levels of failure control, halide induced corrosion issues in wire bonded devices have to be tightly controlled to achieve such a high reliability goal. With real-time corrosion monitoring, for the first time we demonstrated that the explosive H2 evolution coupled with the oxygen reduction reaction, occurring at the critical Al/Cu interfaces, is the key driving force for the observed aggressive corrosion. Several types of passivation coating on Cu wire surfaces to effectively block the cathodic H2 evolution were explored with an aim to disrupt this explosive corrosion cycle. The properties of the protective coating were evaluated using various analytical techniques. The surface coating exhibited high thermal stability up to 260 °C (evaluated using TGA analysis). A uniform, highly hydrophobic coating (surface contact angle of >130° with water), was achieved by carefully controlling CVD parameters such as time of deposition, surface control of Cu metal, amount of inhibitor compound loading, temperature of coating process etc. FTIR spectroscopy combined with corrosion screening was used to optimize the CVD passivated coating with strong chemisorption. SEM and EDX, XPS were carried out on various coated surfaces to understand the composition and selectivity of the film formed through this surface treatment. The surface selective nature of this coating (towards Cu) proved helpful in preventing potential delamination issues during epoxy molding process. The corrosion testing was carried out via HAST testing at 130°C, 2 atm pressure and 100% RH for 48 hours. Delamination analysis and continuity test showed that the inhibitor compound was able to effectively prevent the corrosion even after exposure to harsh HAST conditions.

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Objectif : il a été rapporté que l’utilisation d’agents prophylactiques fluorés pouvait favoriser la corrosion galvanique au sein des alliages de titane. L’objectif de la présente étude était d’évaluer l’effet d’un rince-bouche fluoré sur les propriétés mécaniques de fils en nickel-titane (NiTi) et de fils en cuivre-nickel-titane (CuNiTi) lorsque ces derniers sont couplés à des boîtiers de compositions différentes (boîtiers de marques Smartclip, Clarity, et Sprint). Matériels et Méthodes : 90 segments de fils en NiTi et 90 segments de fils en CuNiTi ont été chacun couplés à 2 boîtiers de chaque marque. Chaque assemblage fil-boîtiers a été par la suite incubé pendant 3 heures à 37°C, soit dans une solution de fluore neutre (Fluorinse™ 0,05% NaF), soit dans une solution de salive artificielle (solution contrôle). Suite à l’incubation, les échantillons étaient nettoyés avec de l’eau déshydrogénée, les fils séparés des boîtiers et montés sur un support pour subir un test de pliage en trois points en milieu humide (salive artificielle) à 37°C. Les modules d’élasticité ainsi que les limites conventionnelles d’élasticité en activation et en désactivation ont été mesurés et comparés. Des analyses de Variance (ANOVA) et des comparaisons post-hoc avec la correction de Bonferronni ont été utilisées pour comparer les groupes entre eux (α = 0,05). Résultats : L’utilisation d’un rince-bouche fluoré a produit une réduction du module d’élasticité et de la limite conventionnelle d’élasticité en activation et en désactivation pour les fils en NiTi ; cependant, cet effet a été modulé par le type de boîtier auquel le fil a été couplé. Les propriétés mécaniques de fils en CuNiTi n’ont pas été affectées par le fluor, ou par le type de boîtier utilisé. Conclusions : L’utilisation d’un rince-bouche fluoré modifie les propriétés mécaniques des fils en NiTi seulement. Cet effet est modulé par le boîtier auquel le fil en NiTi est couplé. A la différence des autres études publiées dans la littérature, nos résultats ne nous permettent pas de conclure que la modification des propriétés mécaniques des fils en NiTi entrainerait obligatoirement un allongement de la durée du traitement orthodontique. Mots clés : Fluor, fils nickel-titane, boîtiers orthodontiques, corrosion galvanique, propriétés mécaniques. / Aim: it has been reported that the use of fluoride prophylactic agents can cause galvanic corrosion of the titanium based alloys used in orthodontics. The purpose of the present study was to investigate the effects of a fluoride mouthrinse on the mechanical properties of nickel-titanium (NiTi) and copper–nickel-titanium (CuNiTi) orthodontic archwires that have been coupled with different types of orthodontic brackets (Smartclip, Clarity, and Sprint brackets). Materials and Methods: 90 segments of NiTi and 90 segments of CuNiTi archwires were tested. Every segment was coupled with 2 brackets of each brand. The wire–bracket assembly obtained was incubated, at 37°C for three hours either in a solution of a commercially available mouthwash (Fluorinse™ 0,05% NaF), or in a solution of artificial saliva (control). Following the incubation, the wires were separated from the brackets, rinsed, mounted on a stainless steel support and placed in a waterbath of artificial saliva at 37°C. A 3-point bending test was made to calculate the loading and unloading elastic modulus and yield strength of the wires. Analysis of variance (ANOVA) and post hoc comparisons were made using Bonferronni’s correction to identify the statistically significant differences (α = 0,05). Results: The use of a fluoridated mouthrinse reduced the loading and unloading elastic modulus and yield strength of the NiTi wires. This reduction, however, varies with the type of bracket that was coupled with the wire. The mechanical properties of the CuNiTi wires were not modified by the use of the fluoride rinse or by the type of bracket to which they were coupled. Conclusions : The use of a fluoride mouthrinse alters the mechanical properties of NiTi wires only. This effect varies with the type of bracket that was in contact with the wire. However our results do not allow us to conclude that the alteration of the mechanical properties of the wires would necessarily imply a prolongation of the orthodontic treatment time. Key words: Fluoride, nickel-titanium archwires, galvanic corrosion, mechanical properties,orthodontic brackets.