Analysis of corrosion in marine and acid environments is a complicated task, involving the interaction of thermodynamic, kinetic and geometrical factors. Two mathematical models which predict corrosion behaviour have been implemented for personal computers. The first program uses an assumption of unidirectional current flow to simplify the prediction of potential distributions for systems of essentially cylindrical geometry containing natural seawater-based electrolytes of differing strength. Using experimentally determined electrochemical and flow rig data, experimental and theoretical results were compared. The correlation between the two was shown to be poor, and this is attributed to the unrepresentative nature of the electrochemical data input to the model. The second model involves the synthesis of polarization curves. Several algorithms to model passivating behaviour have been studied, and one was selected and incorporated into the calculation routine. A number of kinetic and thermodynamic parameters are used in algorithms describing such behaviour, along with activation, concentration and solution polarization effects, for a number of redox reactions, which are then combined to produce an overall potential-log current density curve. Experimentally determined data for pure iron and different stainless steels in marine and acid environments of differing dissolved oxygen content and temperature were obtained. Theoretical models were constructed for each system, and compared to experimental data. Excellent correlation between experimental and theoretical data was obtained for potential ranges in excess of 2 V. Trends in parameter values were discussed, and compared to published data. The transition between stable and unstable passivity of stainless steels was shown to be dependent on the oxygen reduction diffusion limited current density and the iron dissolution reaction free corrosion current density, which in turn was linked to the dissolved oxygen content and temperature of the electrolyte. A new model for the behaviour of stainless steels in the transpassive region was proposed.

L’objectif de ces travaux est de comprendre et modéliser le comportement en corrosion de l’acier Uranus S1N en milieu acide nitrique chaud et concentré. La littérature montre que cet acier présente un comportement en corrosion particulier, en comparaison à d’autres aciers comme l’acier 304L. Les aciers 304L et Uranus S1N ont une composition chimique similaire à l’exception du silicium (moins de 1% pour le 304L et 4% pour l’Uranus S1N). En milieu acide nitrique seul, l’acier 304L présente une vitesse de corrosion plus faible que celle de l’acier Uranus S1N. Cette tendance s’inverse lorsque l’on ajoute des ions oxydants au milieu. Les mécanismes physico-chimiques en jeu ne semblent pas clairement établis. On souhaite comprendre quel est l’effet de l’enrichissement en silicium conduisant à cette différence de comportement. Les phénomènes de réduction et d'oxydation sont comparés entre les deux aciers pour différentes conditions : acide nitrique pur, présence de vanadium pentavalent, présence de chrome hexavalent. On montre que la présence de Si diminue les cinétiques de réduction et donc empêche l'acier Uranus S1N de se trouver dans son domaine transpassif même en conditions très oxydantes. Puis la couche passive de l'acier Uranus S1N est étudiée à travers trois jeux d'expériences. D'une part ses caractéristiques thermodynamiques sont étudiées par la mesure du potentiel d'activation de l'acier. D'autre part, sa composition chimique, sa morphologie et sa structure sont mis en lumière par la correlation de différentes techniques in-situ et ex-situ cohérentes. Enfin, la rupture de passivité à haut potentiel est observée car le Si est suspecté responsable de la disparition de l'attaque intergranulaire. Ces trois axes d'études de l'oxyde protecteur de l'acier Uranus S1N font appel à des techniques in-situ originales comme l'Atomic emission spectro electrochemistry permettant de coupler la mesure électrochimique à l'analyse élémentaire en ligne, mais également à des techniques d'analyses ex-situ telles que la spectroscopie à photoélectrons X ou la spectroscopie d'énergie dispersive sur lame mince. / This work aims at understanding the corrosion behavior of the Uranus S1N stainless steel (SS) in hot and concentratred nitric acid. The Uranus S1N SS is a 304L type SS (18Cr-15Ni) added by 4 wt.% of Si. In pure nitric acid, the 304L SS dissolves slower. In other words, Si enhances the corrosion rate of the SS. But when oxidizing species are added, the 304L dissolves at a much higher rate than the Uranus S1N. Mecanisms involving Si that bring to this phenomenon are not clearly established. The purpose of this thesis project is to elucidate the role of Si in the spontaneous corrosion of the SS in pure nitric acid and in presence of oxidizing species. Reduction and oxydation phenomena are compared, through I-V curves measurements, between both steels, for different conditions : pure nitric acid, presence of pentavalent vanadium, hexavalent chromium. It was shown that Si diminishes the reduction kinetics and prevents the Uranus S1N SS to be shifted to its transpassive domain even when conditions are largely oxidizing. Then the oxide layer was investigated through three sets of experiments. Firstly, thermodynamics of the oxides where characterized by measuring the activation potential of the SS. Secondly, their chemical composition, thickness and structure were investigated coupling congruent in-situ and ex-situ measurements. Eventually, high potential passivity breakdown was investigated to understand why Si inhibits the intergranular attack at the surface. These three investigations rely on coupling original in-situ techniques as the atomic emission spectroelectrochemistry (electrochemical measurements coupled to elemental on line analysis) and ex-situ surface analysis as X-Ray photoelectron spectroscopy or Energy dispersive X-ray spectroscopy on cross-section thin blades.

by Ku, Nim Chung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1997. / Includes bibliographical references. / by Ku, Nim Chung. / Acknowledgment --- p.i / Abstract --- p.ii / Table of contents --- p.iv / List of figures --- p.viii / List of tables --- p.xiv / Chapter Chapter One --- Introduction / Chapter 1.1 --- History of permanent magnet materials --- p.1 / Chapter 1.2 --- NdFeB intermetallic compound --- p.4 / References --- p.8 / Chapter Chapter Two --- Background / Chapter 2.1 --- Corrosion and corrosion control --- p.9 / Chapter 2.1.1 --- Electrochemical mechanisms --- p.10 / Chapter 2.1.2 --- Types of corrosion cell --- p.12 / Chapter 2.1.3 --- Types of corrosion --- p.14 / Chapter 2.1.4 --- Corrosion control --- p.15 / Chapter 2.2 --- Intermetallic compounds and phases --- p.19 / References --- p.26 / Chapter Chapter Three --- Instrumentation / Chapter 3.1 --- Introduction --- p.27 / Chapter 3.2 --- Vacuum evaporator --- p.28 / Chapter 3.3 --- Vacuum furnace --- p.29 / Chapter 3.4 --- Scanning electron microscopy (SEM) & Energy dispersive analysis (EDX) --- p.29 / Chapter 3.5 --- Corrosion chamber --- p.31 / Chapter 3.6 --- Vibrating sample magnetometer (VSM) --- p.31 / References --- p.43 / Chapter Chapter Four --- Moisture corrosion test on a bare NdFeB permanent magnet (without any coating) / Chapter 4.1 --- Introduction --- p.44 / Chapter 4.2 --- Experimental procedures --- p.45 / Chapter 4.3 --- Results from visual inspection --- p.45 / Chapter 4.4 --- Corrosion behavior --- p.46 / Chapter 4.5 --- Measurement of the saturated magnetization --- p.47 / Chapter 4.6 --- The effect of corrosion on the magnetic property of the NdFeB magnet --- p.48 / Chapter 4.7 --- Conclusions --- p.49 / References --- p.57 / Chapter Chapter Five --- Interfacial reaction between the A1 coating and the NdFeB magnet / Chapter 5.1 --- Introduction --- p.58 / Chapter 5.2 --- Experiments --- p.59 / Chapter 5.3 --- The Interaction between the A1 coating and Magnet --- p.60 / Chapter 5.4 --- Conclusions --- p.63 / References --- p.67 / Chapter Chapter Six --- Corrosion behavior of A1 coated NdFeB magnet in moist environment / Chapter 6.1 --- Introduction --- p.68 / Chapter 6.2 --- Experiments --- p.69 / Chapter 6.3 --- Results --- p.69 / Chapter 6.3.1 --- The annealed samples before corrosion test --- p.70 / Chapter 6.3.2 --- Microstructure changes after 3 days of corrosion --- p.70 / Chapter 6.3.3 --- Corrosion process in the annealed samples --- p.71 / Chapter 6.4 --- Corrosion behavior --- p.73 / Chapter 6.4.1 --- Effects of NaCl on the samples --- p.73 / Chapter 6.4.2 --- Effects of the inter-diffusion --- p.74 / Chapter 6.5 --- Conclusions --- p.75 / References --- p.79 / Chapter Chapter Seven --- Dual layer coating of either Ti/Al or Ni/Al on the NdFeB permanent magnet / Chapter 7.1 --- Introduction --- p.80 / Chapter 7.2 --- Experiments --- p.81 / Chapter 7.3 --- The Interaction between the A1 and Magnet --- p.81 / Chapter 7.3.1. --- The Ti/Al coated magnets --- p.82 / Chapter 7.3.2. --- The Ni/Al coated magnets --- p.83 / Chapter 7.4 --- Volume contraction of the intermetallic coatings --- p.84 / Chapter 7.5 --- Conclusions --- p.85 / References --- p.90 / Chapter Chapter Eight --- Conclusions and suggestions for further studies --- p.91

Ce travail de thèse s’intéresse aux alliages à base nickel exposés au milieu primaire des réacteurs à eau pressurisée : ceux-ci, et en particulier, l’alliage 600, contenant environ 16% de chrome, montrent, en service, une sensibilité à un phénomène de corrosion localisée appelé corrosion sous contrainte (CSC). La corrosion sous contrainte aboutit, à terme, au développement de fissures intergranulaires nécessitant le remplacement des matériaux de structure. La compréhension de ces phénomènes constitue donc un enjeu majeur dans le cadre de la sûreté et du prolongement de la durée de vie des réacteurs, avec, également, des aspects économiques évidents. Le rôle de cette étude est d’apporter des éléments de compréhension quant au rôle de l’hydrogène dans ces phénomènes de corrosion sous contrainte. L’objectif de ce travail était double : d’une part, déterminer la source principale de l’hydrogène absorbé par l’alliage lors de exposition au milieu primaire, et d’apporter des éléments permettant de caractériser le mécanisme responsable de son absorption. D’autre part, un second objectif consistait à évaluer dans quelle mesure l’hydrogène absorbé par l’alliage pouvait jouer un rôle dans ces phénomènes de CSC, notamment, en regard de ses interactions possibles avec les défauts de structure du matériau. À cette fin, des techniques de traçage isotopique mises en œuvre lors de la corrosion de ces alliages en milieu primaire ont été utilisées, la pénétration des traceurs étant ensuite analysées par spectrométrie de masse d’ions secondaires. Ces analyses ont permis de montrer que l’hydrogène absorbé provenait principalement de la dissociation de la molécule d’eau lors de l’édification du film d’oxyde passif. Par ailleurs, la création de défauts de structure dans le matériau, et leur étude par annihilation de positons et microscopie électronique en transmission, après création ou après interaction avec l’hydrogène introduit par chargement cathodique, ont permis de caractériser les interactions de cet élément avec les défauts. Ces interactions sont importantes, et mènent à une réorganisation des défauts (coalescence, migration), mais sont transitoires, leur intensité dépendant de l’activité locale de l’hydrogène en solution. Ces résultats ont permis la proposition d’un nouveau modèle d’amorçage et de propagation des fissures de CSC. / Since the late 1960s, a special form of stress corrosion cracking (SCC) has been identified for Alloy 600 exposed to pressurized water reactors (PWR) primary water: intergranular cracks develop during the alloy exposure, leading, progressively, to the complete ruin of the structure, and to its replacement. The main goal of this study is therefore to evaluate in which proportions the hydrogen absorbed by the alloy during its exposure to the primary medium can be responsible for SCC crack initiation and propagation. This study is aimed at better understanding of the hydrogen absorption mechanism when a metallic surface is exposed to a passivating PWR primary medium. A second objective is to characterize the interactions of the absorbed hydrogen with the structural defects of the alloy (dislocations, vacancies…) and evaluate to what extent these interactions can have an embrittling effect in relation with SCC phenomenon. Alloy 600-like single-crystals were exposed to a simulated PWR medium where the hydrogen atoms of water or of the pressuring hydrogen gas were isotopically substituted with deuterium, used as a tracer. Secondary ion mass spectrometry depth-profiling of deuterium was performed to characterize the deuterium absorption and localization in the passivated alloy. The results show that the hydrogen absorption during the exposure of the alloy to primary water is associated with the water molecules dissociation during the oxide film build-up. In an other series of experiments, structural defects were created in recrystallized samples, and finely characterized by positron annihilation spectroscopy and transmission electron microscopy, before or after the introduction of cathodic hydrogen. These analyses exhibited a strong hydrogen/defects interaction, evidenced by their structural reorganization under hydrogenation (coalescence, migrations). However, thermal desorption spectroscopy analyses indicated that these interactions are transitory, and dependent on the local hydrogen activity in the bulk material. Finally, these results allowed a new model describing SCC crack initiation and propagation to be formulated.

Thesis (M.Sc. (Chemistry)) --University of Limpopo, 2018 / The economy of nations depends highly on the industrial products which can be imported or exported. In addition, most industrial equipments such as engineering vehicles, reaction vessels and packaging machineries made from metallic products are prone to corrosion. One of the most efficient ways to mitigate corrosion process is through the use of chemical inhibition method. In this work, unsubstituted (CuPc, NiPc, ZnPc) and substituted phthalocyanines (TNCuPc, TNNiPc, TNZnPc) were synthesised and studied as corrosion inhibitors for aluminium (Al) metal in 1 mol. L-1 hydrochloric acid using gravimetric analysis, potentiodynamic polarisation (PDP) and electrochemical impedance spectroscopy (EIS) techniques. The synthesised inhibitors were characterised for their structure, spectroscopic and thermal properties using X-ray diffraction (XRD), ultraviolet visible (UV-vis), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Both XRD and FTIR indicated a successful synthesis of all inhibitors investigated in the study. Nevertheless, the crystallinity of both ZnPc and TNZnPc was higher as compared to other inhibitors. TGA results showed that NiPc and TNNiPc are most thermally stable amongst the inhbitors studied. The gravimetric data revealed that the inhibition efficiencies decreased with an increase in temperature. Nonetheless, NiPc exhibited the highest inhibition efficiency of 96.42% at 40 ppm as compared to other inhibitors. The PDP results indicated that NiPc, ZnPc, TNNiPc and TNZnPc are mixed-type inhibitors with the exceptions of both CuPc and TNCuPc showing a physisorption adsorption mechanism. The adsorption of the studied inhibitors on Al metal obeyed the Lanmuir adsorption isotherm. The Gibbs free energy indicated that the adsorption process was spontaneous, and that the corrosion inhibition took place by physical adsorption process. / NRF (National Research Foundation)

This thesis mainly concerns the application of electrochemical impedance spectroscopy (EIS) and electrochemical noise analysis (ENA) to the study of CO(subscript)2 corrosion of mild steel and its inhibition. The primary focus is on the use of EIS and ENA to monitor inhibitor film performance and to evaluate inhibitor film persistency.EIS was shown to be a suitable technique to study CO(subscript)2 corrosion product scale, and inhibitor films. The formation and deterioration of protective scales and inhibitor films is found to be accompanied by characteristic spectral changes and a rapid change in electrode impedance. EIS data were used to calculate corrosion related parameters such as the resistances and capacitances of inhibitor layers, and the charge transfer resistance and double layer capacitance. These parameters were used to analyse inhibitor mechanisms, determine corrosion rates and the persistence of inhibitor films.ENA is also a suitable technique to monitor the formation and deterioration of inhibitor films. It has the advantage of being able to monitor rapid processes which occur within one second. Several technical and theoretical developments were made in this thesis including the development of a new method of instantaneous corrosion rate measurement to study fast corrosion processes (the continuous noise resistance calculation method). Experimentally, the noise resistance was confirmed to be similar to linear polarisation resistance in the systems studies. The theoretical background and the advantages and disadvantages of the ENA technique are also discussed.Corrosion product scales formed under different conditions were investigated using EIS and surface analysis techniques. Temperature, pressure and exposure time were confirmed to be the important factors influencing the degree of protection given by the scale. The morphology of corrosion scales ++ / showed an obvious correlation to their protective ability. Electron microscopy revealed two types of crystal structures on corroded steel coupons. The smaller crystals associated with one of these structures was found to contribute most to corrosion protection.Several typical CO(subscript)2 corrosion inhibitors, including an imidazoline and a quaternised amine, were studied by EIS. A multi-layer model was employed to explain the EIS characteristics and self-repairing ability of imidazoline films. A quaternised amine film is most probably a physically or electrostatically adsorbed molecular layer which forms rapidly and desorbs easily.The deterioration of films, formed by commercial batch treatment inhibitors, was found to occur in three stages which were indicated or characterised by Bode phase-angle plots. A method to determine inhibitor film persistency was developed. This method is based on determining the three stages of inhibitor film deterioration, and the continuous measurement of corrosion rate, which is accessible at the second and third stages of film deterioration.

Corrosion of reinforced concrete is the most challenging durability problem that threatens reinforced concrete structures, especially structures that are subject to severe environmental conditions (i.e., Highway Bridges, Marine structures, etc.). Corrosion of reinforcing steel leads to cracking and spalling of the concrete cover and billions of dollars are spent every year on repairing such damaged structures. New types of reinforcements have been developed in order to avoid these high cost repairs. Thus it is important to study the corrosion behavior of these new types of reinforcements and compare them to the traditional carbon steel reinforcements.<p> This study aimed at characterizing the corrosion behavior of three competing reinforcing steels; conventional carbon steel, micro-composite steel (MMFX-2) and 316LN stainless steel, through experiments in carbonated and non-carbonated concrete exposed to chloride-laden environments. Synthetic pore water solutions have been used to simulate both cases of sound and carbonated concrete under chloride ions attack. A three electrode corrosion cell is used for determining the corrosion characteristics and rates. Multiple electrochemical techniques were applied using a Gamry PC4 potentiostat manufactured by GAMRY INSTRUMENTS. DC corrosion measurements were applied on samples subjected to fixed chloride concentration in the solution. EIS measurements were applied on samples subjected to incremental chloride additions. Furthermore, carbon steel rebars embedded in concrete samples pre-contaminated with chloride ions added to the mix will be used to relate corrosion rates inside concrete to those obtained from synthetic solutions and to measure moisture content inside concrete using a nondestructive TDR-based technique.

No description available.

Corrosion of reinforced concrete is the most challenging durability problem that threatens reinforced concrete structures, especially structures that are subject to severe environmental conditions (i.e., Highway Bridges, Marine structures, etc.). Corrosion of reinforcing steel leads to cracking and spalling of the concrete cover and billions of dollars are spent every year on repairing such damaged structures. New types of reinforcements have been developed in order to avoid these high cost repairs. Thus it is important to study the corrosion behavior of these new types of reinforcements and compare them to the traditional carbon steel reinforcements.<p> This study aimed at characterizing the corrosion behavior of three competing reinforcing steels; conventional carbon steel, micro-composite steel (MMFX-2) and 316LN stainless steel, through experiments in carbonated and non-carbonated concrete exposed to chloride-laden environments. Synthetic pore water solutions have been used to simulate both cases of sound and carbonated concrete under chloride ions attack. A three electrode corrosion cell is used for determining the corrosion characteristics and rates. Multiple electrochemical techniques were applied using a Gamry PC4 potentiostat manufactured by GAMRY INSTRUMENTS. DC corrosion measurements were applied on samples subjected to fixed chloride concentration in the solution. EIS measurements were applied on samples subjected to incremental chloride additions. Furthermore, carbon steel rebars embedded in concrete samples pre-contaminated with chloride ions added to the mix will be used to relate corrosion rates inside concrete to those obtained from synthetic solutions and to measure moisture content inside concrete using a nondestructive TDR-based technique.

No description available.