In this study, the corrosion resistance of three different stainless steels (304, 316 and 309) towards eutectic chloride salts is investigated. The performances of two materials to reduce the corrosion of the steels are examined: zirconium as sacrificial anode and an Al2O3 coating deposited by flame spraying. Samples are submitted to a 24 hours corrosion test at 700°C in air. The samples are characterised by weight analysis, SEM observations and EDX analysis of their surface and cross-section. The corrosion resistance of the stainless steels is not improved by adding Zr rods in direct contact with the steel, rather decreased in the areas where the rod laid. However, in these conditions, stainless steel 316 has the best resistance to highly corrosive chloride salts. The Al2O3 coating is too porous and penetrated by the salt, the steel underneath is corroded. Nevertheless, some alumina remains intact after the corrosion test, because of the high inertness of the ceramic. The presence of O2 most certainly accelerated the corrosion mechanism studied here.

Le traitement de la corrosion constitue un enjeu économique, environnemental et de sécurité sanitaire. Plus largement utilisée à l’échelle industrielle, la protection par revêtements consiste à isoler le métal du milieu agressif par une couche adhérente, continue et imperméable. Ils doivent répondre à trois propriétés majeures : 1) être fortement adhérent au substrat métallique, 2) posséder de bonnes propriétés barrière pour limiter la pénétration de l’eau et des espèces agressives et 3) apporter un rôle d’inhibition de la corrosion. Cependant, la protection des surfaces métalliques par les techniques actuelles génère une pollution notable liée à l’usage de chromates. L’utilisation de polymères biosourcés et solubles en milieu aqueux serait un challenge et contribuerait à préserver l’environnement. Les polysaccharides comme le chitosane sont des macromolécules biodégradables et respectueuses de l'environnement possédant des propriétés d’anticorrosion et sont donc des alternatives envisageables. Ces travaux de thèse portent sur le développement de revêtements anticorrosion à base de chitosane. Le chitosane possède deux points faibles pour être utilisé comme revêtement contre la corrosion : 1) une adhésion insuffisante sur la surface des matériaux et 2) un caractère hydrophile. En conséquence, le chitosane a été modifié chimiquement afin d’augmenter son adhésion et ses propriétés barrières. Afin d’améliorer son adhésion sur des substrats métalliques, des groupements de type acide phosphonique ont été ajoutés via la réaction de Kabachnik-Fields sur le chitosane. L’élaboration d’un chitosane possédant des fonctions catéchol a été également discutée. Dans un premier temps, le chitosane modifié a été testé et caractérisé par spectroscopie d’impédance électrochimique (SIE) en tant qu’inhibiteur de corrosion puis des revêtements à partir de ce même chitosane ont été réalisés et leurs protections contre la corrosion ont été évaluées. Deux approches de mise en forme des revêtements ont été testées : par dip-coating et par la technique Layer-by-Layer (LbL). Différentes voies de fonctionnalisation du chitosane ont également été présenté afin d’augmenter les propriétés barrière du revêtement. La chimie de phthaloylation du chitosane a été décrite puis le greffage de chaînes hydrophobes a été étudié. / Corrosion treatment is an economic, environmental and health safety issue. More widely used on an industrial scale, coating protection consists in isolating the metal from the aggressive medium by an adherent, continuous and impermeable layer. They must have three major properties: 1) be strongly adherent to the metallic substrate, 2) have good barrier properties to limit the penetration of water and aggressive species and 3) provide a role in inhibiting corrosion. However, the protection of metal surfaces by current techniques generates significant pollution due to the use of chromates. The use of bio-based and soluble polymers in aqueous media would be a challenge and would contribute to preserving the environment. Polysaccharides such as chitosan are biodegradable and environmentally friendly macromolecules with anticorrosive properties and are therefore possible alternatives. These theses focus on the development of anticorrosion coatings based on chitosan. Chitosan has two weak points for use as a coating against corrosion: 1) insufficient adhesion on the surface of the materials and 2) hydrophilicity. As a result, chitosan has been chemically modified to increase its adhesion and barrier properties. In order to improve its adhesion on metal substrates, phosphonic acid groups have been added via the Kabachnik-Fields reaction on chitosan. The development of a chitosan with catechol functions was also discussed. Initially, the modified chitosan was tested and characterized by electrochemical impedance spectroscopy (EIS) as a corrosion inhibitor and coatings based on the same chitosan were made and their corrosion protection evaluated. Two approaches of coating elaborations were tested: dip-coating and Layer-by-Layer (LbL). Different ways of functionalizing chitosan have also been presented to increase the barrier properties of the coating. Phthaloylation chemistry of chitosan was described and hydrophobic chain grafting was studied.

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.

Le combustible nucléaire utilisé dans les réacteurs actuels doit répondre à une spécification de composition en ²³⁵U différente de celle de l’uranium naturel. Il est alors nécessaire de procéder à un enrichissement en part fissile avant de fabriquer le combustible utilisé en réacteur. Cet enrichissement est réalisé par centrifugation en phase gaz en utilisant l’uranium sous forme d’hexafluorure d’uranium UF₆. Ce composé clé est fabriqué par l’usine COMHUREX à partir de UF₄, et doit répondre à des exigences de pureté, et sa manipulation, à des exigences de sécurité. Cette molécule est très réactive sous forme gazeuse ou liquide et une corrosion du dispositif industriel métallique est constatée. Cette corrosion doit être étudiée afin d’envisager la pollution causée par les produits de corrosion ou encore la durée de vie de l’installation. L’enjeu de cette thèse est de combler les insuffisances de la littérature sur la question de la corrosion par UF₆ liquide à 80°C, qui n’a jusqu’alors pas fait l’objet de recherches publiées. Des équipements adaptés à la réalisation d’essais de corrosion en milieu nucléaire, à 80°C et 3 bars de pression, et des procédures anoxiques d’analyses de ces essais ont dû être mis en place. La réalisation d’essais de corrosion du fer, matériau modèle, par UF₆ liquide à 80°C a ensuite pu être entreprise afin de déterminer la nature des produits de corrosion, la structure de la couche de corrosion et la cinétique de la réaction entre le fer et UF₆ liquide à 80°C. Ces informations ont pu permettre une réflexion sur le mécanisme de corrosion. Ce manuscrit présente le dispositif et la procédure d’essai mise en place permettant la réalisation d’essais de corrosion puis les résultats obtenus. La nature et la structure de la couche de corrosion ont été obtenues grâce aux précautions anoxiques utilisées tout au long des essais réalisés. Deux comportements distincts sont observés. L’origine expérimentale de cette divergence est discutée. La réflexion sur les observations expérimentales, telles que la nature ou les rapports d’épaisseurs des différentes couches, permet de proposer différentes hypothèses sur le mécanisme de corrosion. Un mécanisme de corrosion du fer par UF₆ liquide à 80°C est donc proposé. / The nuclear fuel used in today’s power plants requires a precise uranium isotope composition which is different from natural uranium. Thus, an enrichment process is required, for which gaseous centrifugation is employed using uranium hexafluoride (UF₆). This compound is obtained by fluorination of UF₄ and its handling is submitted to security issues. This compound is highly reactive, in gaseous or liquid state, and the metallic industrial production setup is corroded, leading to solid residues at process temperatures. This corrosion has to be considered in order to predict both the process efficiency (purity, output) and the resulting industrial issues (setup lifetime, corking). This study aims at understanding liquid uranium hexafluoride corrosion at 80°C, which remains unstudied to this day. A dedicated novel test setup along with adapted analysis precautions have been developed in order to perform reliable experiments and corrosion products identification, since those products and UF₆ are moisture sensitive. This study mostly focused on the corrosion of iron as a model material in liquid UF₆. The experimental results obtained, allowed us to follow the evolution of the structure and the nature of the corrosion layer. Two different kinds of layer have been observed and the experimental origin of this divergence is discussed. With those experimental results, a corrosion mechanism is suggested for the corrosion of iron in liquid uranium hexafluoride at 80°C.

Bibliography: pages 96-103. / The mechanisation of the working stapes in South African gold mines has required the introduction of a fundamentally new technology, hydro-power, in which machines are powered hydraulically using mine water fed from above ground. Mine water is aggressive and has a variable acidity and pH, and contains high concentrations of sulphate, chloride and nitrate ions. In order to minimise the pitting corrosion of piping and stoping machinery a compromise between selecting a suitable corrosion resistant material and treating the mine water to an acceptable level of corrosiveness is being sought.

Corrosion characteristics of seven varieties of metals—zinc, brass C260, stainless steel 302, stainless steel 316, stainless steel 420, stainless steel 430, and stainless steel 440—in three aqueous media—Atlantic Ocean, Charles River, and deionized waters—were assessed via mass loss methods over 32 weeks, with supplemental data in the form of photomicrographic records. Concurrently, tests were conducted to determine the degree of measurement error resulting from the analytical scale used during corrosion assessment. This was accomplished by using reference samples of each type of metal and a glass vial as the container that held the metal and water samples. These error tests indicated that while the mass error associated with the metal samples was low, the error in mass associated with the vial displayed error margins two orders of magnitude larger than the error margins for the smaller metal samples. Further, control tests and statistical analysis indicated that this variation was the result of some quality inherent to the vial. The metal samples involved in the corrosion assessment experiment generally displayed corrosion characteristics in agreement with trends reported in the literature. Zinc produced the greatest quantity of corrosion residues out of all the metals studied. Brass C260 also developed visible corrosion. For example, brass C260 developed dark green/brown adherent residue and whitish blue-tinted nonadherent residue in Atlantic Ocean water, faint greenish tarnishing and some dark green spots and dots over time in Charles River water, and only faint greenish tarnish in deionized water. In contrast with zinc and brass C260, the stainless steels did not exhibit signs of significant corrosion rates excepting stainless steel 420 (SS420), which displayed pitted features surrounded by multi-colored rings on all of its Atlantic Ocean immersion samples and 25% of its Charles River immersion samples. Atlantic Ocean water generally caused the greatest degree of corrosion for all metals, followed by Charles River water, then deionized water, except in the case of zinc. Residues found on zinc samples immersed in the three different water types were similar to each other in coloration. SS420 samples immersed in different waters also displayed similar-colored residues. Comparisons between the corrosion features of SS420 and the single stainless steel 430 and 440 samples that did show visible corrosion in Atlantic Ocean water suggested that minor compositional variations between stainless steels have little effect on the visual characteristics of the corrosion residues they form. Corrosion rates were calculated using linear regressions of the mass loss data for all metal sample sets. While some of these corrosion rates approached literature-reported values for the metal in question, the distributions of the mass loss data sets indicated that any mass changes that resulted from corrosion were likely too small for the electronic scale to detect. Consequently, it is recommended that future corrosion studies using the mass loss method utilize metal samples similar in size to objects typically found at crime scenes.

A dissertation submitted in fulfilment of the requirement for the degree of Master of Science in Engineering, to the Faculty of Engineering and the Built Environment, School of Chemical and Metallurgical Engineering, University of the Witwatersrand, Johannesburg, 2018 / The two hydrofluoric acid (HF) storage tanks used for holding 70% technical grade HF product at the HF plant at Necsa started leaking in March 2012. An evaluation of the failure was conducted in the form of a corrosion failure analysis. It was confirmed that a higher than usual nitric acid (HNO3) content in the technical grade HF stream changed the corrosion mechanisms typically experienced within the HF storage vessels, which then caused the tanks to fail. Immersion type corrosion experiments were done to safely simulate the corrosive environment experienced by the mild steel, stainless steel and nickel alloys used on site, and to predict the change in corrosion rates and characteristics associated with the HNO3 contamination in the HF production plant circuit. Since the corrosion resistance of mild steel in HF is heavily dependent on the thickness of the protective scale on the steel, a series of planned interval corrosion tests (PICTs) was done to reproduce and then examine the oxidefluoride barrier on mild steel coupons in pure 70% HF prior to corrosion tests. These shorter PICTs were also done on the stainless steel and nickel alloys and showed that the prepassivation step had a surface cleaning effect when exposed for only 24 h. Eleven day corrosion tests were conducted to establish the effect of HNO3 concentration and temperature on mild steel corrosion in 70% HF, and to determine the change in corrosion rates and mechanisms associated with HNO3 contamination (0.1-1% HNO3) of the downstream HF products. The corrosion was characterized by analysing the corroded coupons for mass loss, apparent corrosion rates, acid consumptions, visual observations of scale formation and pits, as well as depth profiles from scanning electron microscopy and energy dispersive spectroscopy analyses. Linear relationships were frequently observed when analysing mass losses for the coupons over time, making it possible to define corrosion rates in terms of first order reaction kinetics. The harshest corrosive condition for mild steel in HF was determined to be 1% HNO3 in 70% HF at a constant temperature of 25ºC. The corrosion characteristics of alloys used in the HF plant, as affected by HNO3 impurities (in the range 50–10000 ppm) in the final HF acid product (70% Technical grade) were successfully established. Normalized SA516 Grade 70 mild steel and Monel 400 were found not adequate for use as construction materials in a plant where HNO3 contamination was >100 ppm. However, the corrosion resistance of SS 904 L was suitable under these conditions and was recommended for applications in HF solutions where the presence of an oxygen-containing acid (e.g. HNO3) is consistent. It was recommended that Alloy 31, Alloy 33 or Nirosta 4565S, with higher chromium content (>20 wt% Cr), should be considered for construction material of the HF plant when HNO3 contamination becomes unavoidable. However, if the continued use of mild steel at the plant cannot be avoided, other inhibition strategies tailored to the selective consumption of HNO3 in the HF product stream need to be investigated. / XL2019

All-aluminum microchannel heat exchangers are designed to significantly reduce refrigerant charge requirements, weight, reduced brazed joints, and decreased potential for leakage by increasing reliability. Al 3003 alloy is corrosion resistant and can be formed, welded, and brazed but the issue with all-aluminum heat exchangers is localized corrosion (pitting) in corrosive environments. Currently, there is no universally accepted corrosion test that all coil manufacturers use to characterize their products. Electrochemical testing method of cyclic polarization was employed in this investigation and relevant parameters including electrolyte corrosive agent and its concentration, electrolyte pH, and applied potential scan rate was varied to find an optimal set of parameters. Results of cyclic polarization of Al 3003 in electrolytes containing various concentrations of NaCl were compared with those of the tests in Sea Water Acidified Accelerated Test (SWAAT) electrolyte and it is shown the SWAAT electrolyte (4.2% sea salt acidified to pH of 2.9) is by far stronger (in terms of corrosivity) than typical 3.5% NaCl solution used in most corrosion testing. Corrosion rates (g/m2yr) of Al 3003 measured in this investigation were comparable to those provided by ISO 9223 standard corresponding to C1 through CX categories. Duration of cyclic polarization test is much shorter than that of SWAAT and results obtained in this test is more reproducible compared to those of SWAAT. Scanning electron microscopy micrographs show typical pit depths of about 50 μm.

This dissertation proposes a multiscale Internal State Variable (ISV) inelasticity-corrosion damage model that is motivated by experimental microstructure-property relations of magnesium alloys. The corrosion damage framework was laid out based on observation of different corrosion mechanisms occurred on an extruded AM30 magnesium alloys. The extruded AM30 magnesium alloy was studied under two corrosion environments (cyclical salt spray and immersion) in order to observe the corrosion rates under different exposure environments. The coupons were examined at various times to determine the history effects of three corrosion mechanisms: (1) general corrosion; (2) pitting corrosion in terms of the nucleation rate, growth rate, and coalescence rate; and (3) intergranular corrosion. The multiscale ISV corrosion model was developed by bridging the macroscale corrosion damage to the mesoscale electrochemical kinetics, microscale material features, and nanoscale material activation energies. The corrosion testing results of Mg alloys (pure Mg, Mg-2% Al, and Mg-6% Al) were used to develop, calibrate, and validate the model, and good agreement was found between the model results and the corrosion testing data. Finally, the simultaneous effects of corrosion and cyclic loading were tested but not modelled for the extruded AM30 magnesium alloy by conducting fatigue experiments in a 3.5 wt.% NaCl solution environment. The corrosion fatigue life of the AM30 alloy was significantly reduced due to corrosion pit formation on specimen surface, hydrogen diffused into the material , and the fracture surface dissolved into the solution. The corrosion damage that arose on the fatigue specimens reduced the crack nucleation process and enhanced the crack propagation rate.

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.