The thesis focuses on the corrosion research of AlCu4Mg1 aluminium alloys of square shape and sheet metal coated in 99.5% aluminium. The theoretical part deals with the characteristics of aluminium, the classification and naming of aluminium alloys and the impact of admixtures on aluminium alloys. In the following chapter a general introduction to metal corrosion, its differentiation according to the type of corrosion attack, mechanisms of corrosion, the impact of corrosive environment, according to the choice of anti-corrosion protection, etc. is given. The main part is devoted to the corrosion of aluminium with a special importance of the impact of admixtures on aluminium alloys, the types of corrosion attack, the impact of corrosive environment as well as of the anti-corrosion protection of aluminium alloys. The corrosion tests in controlled atmosphere are considered in the next chapter, while the last one deals with the evaluation methodology of the process of corrosion. At the beginning of the experimental part all the used samples and materials are introduced. The thesis continues then with an overview and a description of the methods used for experiments. The measurement procedure and the results of the experiments are presented in the following chapter that focuses on the metallographic analysis of the aluminium alloy samples before the experiment and after the corrosion attack. The main part of the chapter deals with the dependence of corrosion speed of the individual aluminium alloy samples on time after being exposed in the climate chamber and the salt fog chamber

Diploma thesis is worked-up as a part of master’s studies of engineering technology M2I – K, analyzing the possible methods of surface treatment of spherical pin, that increase its corrosion resistance. Spherical pin is mounted into several types of chassis components such as joints, control arms, etc. The current situation is inconvenient for manufacturers, insufficient corrosion protection increases the number of complaints and this may be reflected in the number of future orders. Via of suitable surface treatment is to achieve a higher corrosion resistance while maintaining the functional properties of pins used.

This master thesis describes design of suitable surface treatment technology to get component resistant to corrosion of conventional atmosphere. Given component has a shape of pin and is made of construction steel. At the beginning, there is a theoretical study of galvanic zinc coating and galvanic surface treatment in general. Then there is analysis of damaged galvanic zinc surface and its impact of corrosive resistance of that layer with collaboration with company KOZÁK SVITAVY. Corrosive resistance of damaged zinc layer is then compared with corrosive resistance of quality zinc layer. At the end of this thesis is technical and economic evaluation.

This study was intended to provide a fuller understanding of the surface chemical processes which result in the corrosion of ferrous materials.

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Today there are numerous methods to slow down a corrosion process of metallic materials. However, due to environmental effects and health risk issues, several traditional corrosion inhibitors have to be phased out. Hence, it is of great importance to develop new corrosion inhibitors that are “green”, safe, smart and multifunctional. In this essay, the focus is on mussel adhesive protein (MAP) and its possibility to reduce the rate of the corrosion process. The protein exhibit great adhesive strength and protective properties, allowing it to adhere to a multitude of different surfaces and is therefore of great interest of corrosion science. The protein Mefp-1, derived from the blue mussel´s foot, had been pre-adsorbed on the carbon steel surface and provided good corrosion inhibition in a basic chloride solution for a short exposure time. The protection was further improved with the assist of iron and ceria ions by formation of protein/ions complexes within the surface films and thus enhanced the corrosion protection for longer exposure time. Ceria nanoparticles were used in order to create a multi-layer composite film with an even higher corrosion protection. The results suggest a denser film compared to previous samples and a more uniform surface.

In a previous project, mobile exposures in road environments have been performed in various areas of the world. A number of materials and coatings have been attached under trailers which travels long distances in different types of road environments. One of the materials, zinc, demonstrated various corrosion rates in different parts of the world. In this investigation two various accelerated corrosion tests have been performed at the laboratory of Swerea Kimab in order to realize parameter influence on zinc. Even though the corrosion rates are known, the relation to formed corrosion products has not been investigated earlier. In the present study, corrosion products on zinc have been analyzed using XRD and FTIR. The results from analyses of formed corrosion products have been evaluated together with measured corrosion rates, both from the mobile exposure and the accelerated tests, in order to try to understand under what conditions certain corrosion products are formed and how it affects the corrosion rate. A cold humid climate was found to be the most corrosive. In these environments, de ‐icing salts are used which promotes formation of Simonkolleite and in a subsequent step; Gordaite (if there is a not negligible deposition rate of SO2/SO42‐) which is often observed as the end product in marine environments.

Les connecteurs clips utilisés pour assembler les tubes de riser pour le forage pétrolier offshore subissent un chargement cyclique dû aux vagues. 90% de la durée de service est passée en mode connecté, avec une contrainte moyenne élevée, alors que 10% est passé en mode déconnecté, avec une faible contrainte moyenne. Des calculs numériques montrent qu’un chargement cyclique de tension biaxiale en phase prévaut dans la zone critique de la structure. Les effets de contrainte moyenne et de biaxialité doivent tous deux être pris en compte pour un design approprié. Les critères de fatigue multiaxiale de la littérature sont basés sur des données de traction-torsion et ne discriminent pas bien l’influence de la tension biaxiale de celle d’une contrainte moyenne. Un des objectif de cette étude est donc de caractériser séparément ces deux effets.Pour étudier les effets de contrainte moyenne, des essais de fatigue uniaxiale ont été menés avec différents rapports R. Les durées de vie diminuent avec l'augmentation de R, et la limite d'endurance suit la parabole de Gerber. À faible contrainte moyenne et amplitude de contrainte élevée, les fissures s’amorcent en surface, tandis que pour des rapports R élevés et des amplitudes faibles, les fissures s’amorcent à partir de défauts internes ou coupant la surface. Cette transition est analysée à partir de calculs élasto-plastiques des champs de contrainte et déformation autour des défauts. Les fissures internes se propagent sous un faible ΔK indépendant de R, ce qui est attribué à la quasi absence d’effets de fermeture.Pour étudier l'effet de biaxialité, des essais cycliques de tension et pression interne combinées en diverses proportions ont été effectuées à rapport R fixe (0,25). Un taux de biaxialité modéré (B = 0,25 et 0,5) a un effet bénéfique, attribué à un retard de l'amorçage des fissures, alors que la tension équibiaxiale a un effet légèrement nuisible, attribué à un "pseudo effet de taille" (probabilité plus grande qu’une microfissure se propage le long de deux plans principaux équivalents, au lieu d’un seul).De facettes intergranulaires révélatrices de fragilisation par l'hydrogène ont été observées sur les surfaces de rupture. L’évolution de leur fraction avec ΔK et la biaxialité suggèrent une réduction de la vitesse de fissuration à B≤0.5, mais l'effet néfaste de la tension équibiaxiale ne peut être attribué à une accélération de la propagation.Plusieurs des critères de fatigue existants échouent à décrire toutes les données de cette étude. Les critères d'endurance avec un terme linéaire de contrainte moyenne ou de tension hydrostatique ne parviennent pas à prédire les variations de la limite d'endurance. Un nouveau critère de fatigue a été proposé sur la base de la parabole de Gerber. Il décrit bien les effets combinés d'une contrainte moyenne et d’un taux de biaxialité positif.Des essais biaxiaux ont également été effectués dans l’eau salée (3.5% NaCl) pour étudier l'influence de ce milieu sur les durées de vie en fatigue, en corrosion libre et avec une protection cathodique qui amplifie le dégagement d’hydrogène.En corrosion libre, l'eau salée réduit fortement les durées de vie et supprime la limite d'endurance. Cela est dû à la formation de piqûres de corrosion qui favorisent l’amorçage précoce et multiples de fissures. La tension équibiaxiale n’accentue pas l’effet nocif de l'eau salée, malgré des mécanismes de fissuration différents: décohésion fragile transgranulaires en tension uniaxiale, mais principalement intergranulaire en tension biaxiale.La protection cathodique annule l'effet néfaste de l'eau salée pour tous les taux de biaxialité, en dépit d'un net accroissement de la fragilisation par l’hydrogène des joints de grains. Les surfaces de rupture deviennent presque entièrement intergranulaire, tandis qu’à l'air, le taux de rupture intergranulaire ne dépasse pas 45%. / The clip connectors used to join the riser tubes for offshore oil drilling undergo cyclic loading due to sea waves. 90% of the service life is spent in the “connected mode” with a high mean stress and 10% in the “disconnected mode” with a lower mean stress. Finite element computations revealed in-phase biaxial tension in the critical areas of the clip connector along with high mean stresses. Thus, both the mean stress effect and the biaxiality effect need to be addressed for proper design of these structures. However, most of the multiaxial fatigue criteria are based on tension-torsion fatigue data and do not discriminate the influence of biaxial tension from that of a mean stress. This study investigates separately these two effects.For investigating the mean stress effect, uniaxial fatigue tests were run on Cr-Mo steel with various R ratios (σmin/σmax). The fatigue lives, as well as the slope of the S-N curves were found to decrease with increasing R, and the endurance limit to follow Gerber’s parabola. At low R ratios and thus relatively high stress ranges, fatigue cracks initiated from the surface, while for high R ratios, and thus low stress ranges, cracks initiated from internal or surface-cutting defects. This transition was analyzed based on elastic-plastic computations of stress-strain fields around the defects. The threshold for internal fatigue crack growth from defects was found to be quite low and independent from the R ratio. This was attributed to a nearly closure-free propagation.To investigate the effect of positive stress biaxiality, combined cyclic tension and internal pressure tests with various proportions of each loading were run on tubular specimens, at fixed R ratio (0.25). Moderate stress biaxialities (B= 0.25 and 0.5) had a beneficial effect on fatigue lives, attributed mainly to a retardation of crack initiation, while equibiaxial tension had a slightly detrimental effect, attributed to a “pseudo size effect” (higher probability for an incipient crack to grow along two possible planes, compared to a single one).Intergranular facets associated with temper and H2 embrittlement were observed on the fracture surfaces. The evolutions of their surface fraction with ΔK and load biaxiality suggested a possible reduction in crack growth rate at moderate biaxialities, but the detrimental effect of equibiaxial tension could not be explained in terms of crack growth rate.Several popular fatigue criteria failed to describe all fatigue data. Endurance criteria that include a linear mean stress term or contain a hydrostatic tension term fail to predict the variations of the endurance limit of this material with the R ratio and biaxiality ratio. Thus, a new fatigue criterion based on Gerber’s parabola was proposed. It captured the evolution of the endurance limit under the combined effects of positive mean stress and biaxiality.Similar tests were run to investigate the influence of salt water (3.5% NaCl) on fatigue lives under two types of test conditions: 1) free corrosion and 2) cathodic protection.In free corrosion, salt water strongly reduced the fatigue lives and suppressed the endurance limit. This was due to the formation of corrosion pits that favor early, multiple crack initiations. The detrimental effect of salt water was not enhanced by equibiaxial tension, which did not modify the size and density of corrosion pits. Fatigue lives in uniaxial and biaxial tension were nearly the same, although the crack growth mechanism was different: transgranular brittle decohesion in uniaxial loading and mostly intergranular in biaxial tension.Cathodic protection cancelled the detrimental effect of salt water for all biaxialities, in spite of a clear enhancement of H-induced embrittlement of the grain boundaries. The fracture surfaces were nearly fully intergranular, irrespective of load biaxialities, while in air the proportion of intergranular fracture was less than 45%.

As multistep, multilayer processing in semiconductor industry becomes more complex, the role of cleaning solutions and etching chemistries are becoming important in enhancing yield and in reducing defects. This thesis demonstrates successful formulations that exhibit copper and tungsten compatibility, and are capable of Inter Layer Dielectric (ILD) cleaning and selective Ti etching. The corrosion behavior of electrochemically deposited copper thin films in deareated and non-dearated cleaning solution containing hydrofluoric acid (HF) has been investigated. Potentiodynamic polarization experiments were carried out to determine active, active-passive, passive, and transpassive regions. Corrosion rates were calculated from tafel slopes. ICP-MS and potentiodynamic methods yielded comparable Cu dissolution rates. Interestingly, the presence of hydrogen peroxide in the cleaning solution led to more than an order of magnitude suppression of copper dissolution rate. We ascribe this phenomenon to the formation of interfacial CuO which dissolves at slower rate in dilute HF. A kinetic scheme involving cathodic reduction of oxygen and anodic oxidation of Cu0 and Cu+1 is proposed. It was determined that the reaction order kinetics is first order with respect to both HF and oxygen concentrations. The learnings from copper corrosion studies were leveraged to develop a wet etch/clean formulation for selective titanium etching. The introduction of titanium hard-mask (HM) for dual damascene patterning of copper interconnects created a unique application in selective wet etch chemistry. A formulation that addresses the selectivity requirements was not available and was developed during the course of this dissertation. This chemical formulation selectively strips Ti HM film and removes post plasma etch polymer/residue while suppressing the etch rate of tungsten, copper, silicon oxide, silicon carbide, silicon nitride, and carbon doped silicon oxide. Ti etching selectivity exceeding three orders of magnitude was realized. Surprisingly, it exploits the use of HF, a chemical well known for its SiO2 etching ability, along with a silicon precursor to protect SiO2. The ability to selectively etch the Ti HM without impacting key transistor/interconnect components has enabled advanced process technology nodes of today and beyond. This environmentally friendly formulation is now employed in production of advanced high-performance microprocessors and produced in a 3000 gallon reactor.