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Made available in DSpace on 2014-10-09T12:36:50Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:00Z (GMT). No. of bitstreams: 1 04366.pdf: 5734662 bytes, checksum: 226af9141e1984ce9dff1230b5f437ed (MD5) / Tese (Doutoramento) / IPEN/T / University of Manchester, England

Electrodepositable paints are used in the auto industry to provide the majority of the protection against corrosion to mild steel car body shells. They are generally epoxy/blocked isocyanate resins systems which are applied by action of an electropotential between the car and an anode. Upon heating to 175°C the blocked isocyanate deblocks, and crosslinking occurs predominantly via the formation of urethane and urea linkages. The aim of the project was to gain a better understanding of the factors which may affect the adhesion of the electrocoat resin polymer to a steel surface, to investigate possible replacements for the tin catalyst currently used, and to develop a quantitative mechanical test for paint adhesion. This was achieved by employing various analytical techniques including Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC) and mechanical testing.

Niobium is well known for its excellent corrosion resistance based on the formation of a stable passive oxide layer, which protects the metal against corrosion in most aqueous media and makes it an interesting candidate for corrosion resistant coating applications. However, deposition of Nb films is restricted to few technologies and difficulties arise from the toxic nature of the electrolytes employed in electrodeposition of Nb, the high reactivity of the metal with residual gases in vacuum plasma spraying and its high melting point (Tm = 2500 0C) in PVD deposition. The present thesis describes the development of corrosion resistant Nb coatings on stainless steel and brass substrates by the combined steered arc/unbalanced magnetron sputtering technique. Evaluation of the corrosion behaviour is performed by potentiodynamic polarisation measurements in 3% NaCl. It is shown that corrosion resistant Nb coatings, with passivation characteristics similar to that of bulk Nb, can be produced on stainless steel substrates by unbalanced magnetron sputtering at a low deposition temperature (T = 250 0C) under reduced ion bombardment. However, the ion etching pre-treatment of the substrate prior to deposition has a significant influence on the corrosion resistance of the coating/substrate system. The employed polarisation measurements reveal that a fully passive and protective behaviour could only be achieved if Nb ions from the cathodic arc source are chosen as the etching species. In contrast, coatings deposited after Cr ion etching from the arc source and inert Ar ion etching, utilising a glow discharge, exhibit localised breakdown and pitting of the substrate. Cross sectional TEM imaging and STEM-EDX analyses reveal that bombardment of the stainless steel substrate by the multiply charged Nb ions generates a compositionally intermixed, very fine crystalline or "amorphised" interface layer, with a thickness of ~3-8nm, depending on the Nb ion energy. It is proposed that this layer acts as an additional barrier against corrosion due to (i) the structural homogeneity achieved by amorphisation and (ii) chemical stabilisation due to the introduction of Nb in the near surface region. The energy of the bombarding Nb ions, i.e. the substrate bias voltage during the etching stage, was found to further influence the corrosion resistance. Best results are achieved with "medium" bias voltages in the range of -600V to -800V, which is believed to be due to an optimum combination of structural and chemical protection mechanisms. The fully passive corrosion behaviour could not be observed in the case of brass substrates. However, the PVD coating systems on brass and on stainless steel are superior, in the employed polarisation measurements, to commercially produced, electroplated Cr, Ni and Ni/Cr coatings on the same substrate materials. Other coating properties investigated in the present study include microstructure, hardness, crystallographic orientation and residual film stresses.

Made available in DSpace on 2014-10-09T12:36:50Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:56:00Z (GMT). No. of bitstreams: 1 04366.pdf: 5734662 bytes, checksum: 226af9141e1984ce9dff1230b5f437ed (MD5) / Tese (Doutoramento) / IPEN/T / University of Manchester, England

Coal-tar was commonly used as an internal lining for corrosion protection of water pipes from the 19th century up to the present. It is reported that these coatings can lead to elevated concentrations of Polycyclic Aromatic Hydrocarbons (PAHs) in the distributed drinking water. The aim of the project was to investigate the processes and mechanisms responsible for the occurrence of these substances in drinking water distribution systems. The results presented in this project showed that the occurrence of PAHs in a distribution system was linked to the presence of the disinfectants chlorine and chlorine dioxide. This dependence could be shown in the laboratory, in a pilot-scale pipe rig as well as in field investigations in a real distribution system. Generally, hostile environmental conditions for microbiological activity such as stagnation periods and anaerobic conditions could be identified as the most important factors to favour the occurrence of PAHs in the drinking water. It was clearly shown that disturbances in the hydraulic regime such as water hammers, operation of valves and rapid increases in flow velocity can result in enhanced PAH concentrations. Immediately after stagnation periods PAH concentrations increased to levels which exceeded the prescribed concentrations of the EC-guideline of 200 ng/l. In laboratory experiments it was demonstrated that the coal-tar is a substrate for the growth of biofilms. Batch experiments and reactor experiments showed that the removal of biofilm resulted in a higher leaching rate of the PAHs into the water. Experiments concerning the potential for the formation of chlorinated PAHs as disinfection by-products from the PAHs prevalent in water distributed through coal-tar lined pipes showed that their occurrence is very unlikely under conditions prevalent in water distribution systems. A theory is presented which indicates that particles adhering to the pipe walls which can be sometimes embedded in the biofilm matrix represent a major factor in the process of the mobilisation of PAHs. The destabilisation of the biofilm matrix by hostile environmental conditions (disinfectants, aerobic conditions, oxygen limitation during stagnation periods) or enhanced shear forces on the biofilm, results in the release of particles highly contaminated with PAHs.

As an important technique for corrosion control in marine environment, Cathodic Protection (CP) should be applied with a full understanding of environmental conditions and a good consideration of current requirements. Early studies on different kinds of steel specimens in the intertidal zone show severe corrosion losses. Nevertheless, there is evidence that CP can work in these regions of a steel structure because electrolyte pathway can remain some time on thin wetted surfaces when tides recede. This research aims to study corrosion activities and their behaviour under the influence of CP in a thin layer of electrolyte as a simulation of the inter-tidal zone. By means of a mechanical vibrating probe, Scanning Vibrating Electrode Technique (SVET) may be used to study local activities at coating defects in a thin electrolyte layer. The effect of CP on the local currents at the defect site was confirmed by SVET and, significantly, the development of calcareous films under these conditions in seawater was also observed. Such films are found to be effective in the absence of cathodic polarisation and only failed after damage. In order to explore the performance of applying CP, a Finite Element (FE) model of electrically connected zinc and steel samples beneath a specific thickness of electrolyte has been created, with full polarisation curves implemented for each metal based on experimental results obtained. The influence of the electrolyte conductivity and the geometry of the electrodes has also been considered. A comparison can then be made between experimental investigation and computational modelling of this corrosion cell. Epoxy-coated and uncoated mild steel samples obtained in the simulated tidal facility were also investigated. The formation of calcareous films was confirmed. Calcareous films were protective under these intermittent wetting conditions. Techniques used to understand the performance include optical observation, Scanning Electron Microscopy (SEM) together with Energy Dispersive X-ray (EDX) and X-ray Diffraction (XRD) analysis.