<p>Thin films prepared by electrochemical and physical vapor deposition (PVD) methods were investigated for corrosion protection of metals and alloys. Various electrochemical methods were developed, such as electrophoretic deposition (EPD), electrolytic deposition (ELD) and combined methods. EPD method has been developed for the deposition of polymer films, including poly(2-vinylpyridine) (PVP) and co-polymer poly(4-vinylpyridine-<em>co</em>-butyl methacrylate) (PVPBM). The method involved the electrophoresis of protonated polymer macromolecules, base generation at the cathode surface, charge neutralization and deposition of water insoluble polymer films. Nanostructured CeO₂ films were prepared by cathodic ELD and EPD. Cathodic ELD involved electrosynthesis of CeO₂ nanoparticles in the cathodic reaction and film formation. New dispersion agents were developed for CeO₂ particles for application in EPD processes. The kinetics of ELD and EPD and deposition mechanisms were investigated.</p> <p>Composite polymer-CeO₂ films were deposited using various strategies, based on ELD or EPD of CeO₂ and EPD of polymers. The composite films were deposited as monolayers, multilayers or materials of graded composition. The deposition yield and film composition can be varied.</p> <p>The composite films were studied by electron microscopy, X-ray diffraction, thermogravimetric and differential thermal analysis. Electrochemical testing showed that polymer and composite films provided corrosion protection of stainless steel substrates.</p> <p>Corrosion protection properties of coatings deposited on commercial AMPCO and TZM alloys was investigated. CrN, CrN-D, and TiC were deposited by PVD method. Ni coatings were deposited by electroplating. The analysis of Tafel plots and impedance spectroscopy data showed that CrN and CrN-D coatings deposited by PVD showed better corrosion protection of AMPCO and TZM alloys, compared to TiC and Ni coatings. The results of this investigation pave the way for the fabrication of novel coatings with advanced corrosion protection, wear and mechanical properties, using combined PVD and electrochemical methods.</p> / Master of Applied Science (MASc)

ABSTRACT HYDROGEN STORAGE IN MAGNESIUM BASED THIN FILMS Akyildiz, Hasan Ph.D., Department of Metallurgical and Materials Engineering Supervisor : Prof. Dr. Tayfur &Ouml / zt&uuml / rk Co-Supervisor : Prof. Dr. Macit &Ouml / zenbas October 2010, 146 pages A study was carried out for the production of Mg-based thin films which can absorb and desorb hydrogen near ambient conditions, with fast kinetics. For this purpose, two deposition units were constructed / one high vacuum (HV) and the other ultra high vacuum (UHV) deposition system. The HV system was based on a pyrex bell jar and had two independent evaporation sources. The unit was used to deposit films of Mg, Mg capped with Pd and Au-Pd as well as Mg-Cu both in co-deposited and multilayered form within a thickness range of 0.4 to 1.5 &mu / m. The films were crystalline with columnar grains having some degree of preferred orientation. In terms of hydrogen storage properties, Mg/Pd system yielded the most favorable results. These films could desorb hydrogen at temperatures not greater than 473 K. The study on crystalline thin films has further shown that there is a narrow temperature window for useful hydrogenation of thin films, the upper limit of which is determined by the intermetallic formation. The UHV deposition system had four independent evaporation sources and incorporated substrate cooling by circulating cooled nitrogen gas through the substrate holder. Thin films of Mg-Cu were produced in this unit via co-evaporation technique to provide concentrations of 5, 10 and 15 at. % Cu. The films were 250-300 nm thick, capped with a thin layer of Pd, i.e. 5-25 nm. The deposition was yielded nanocrystalline or amorphous Mg-Cu thin films depending on the substrate temperature. At 298 K, the films were crystalline, the structure being refined with the increase in Cu content. At 223 K, the films were amorphous, except for Mg:Cu=95:5. The hydrogen sorption of the films was followed by resistance measurements, with the samples heated isochronally, initially under hydrogen and then under vacuum. The resistance data have shown that hydrogen sorption behaviour of thin films was improved by size refinement, and further by amorphization. Among the films deposited, amorphous Mg:Cu=85:15 alloy could absorb hydrogen at room temperature and could desorb it at 223 K (50 &ordm / C), with fast kinetics.

We have reported the optical properties of isolated gold nanowires and of nanowire arrays. Despite the advantages gold has to offer as it is less sensitive to oxidation and as an biocompatible metal, it has been scarcely studied than silver or semiconductors nanowires. We have made surface enhanced Raman spectroscopic (SERS) studies on the isolated nanowires and nanowire arrays. Single molecule regime is attained and has been proven with the aid of two dye molecules that are co-deposited. The propagation of surface plasmons in these nanowires and their evolution with the excitation wavelength have been studied. We report a propagation distance of 3.8 µm which is longer than the values previously reported in literature. Nanowire arrays have been investigated with two dyes again to disentangle the various factors contributing to SERS. Polarization studies and the evolution of enhancement in the nanowires with the wavelength have been reported and explained with the aid of simulations obtained by the discrete dipole approximation (DDA). The scanning near field optical microscopy (SNOM) has been done to investigate the local field enhancements on the nanowire arrays. Two different polarizations and two excitation wavelengths have been used. The original idea of the technique includes the use of two illumination modes which serves two purposes. One, to map the regions of enhanced field and the other to study the propagation effects seen on the nanowire.

Les tokamaks visent à réaliser la fusion contrôlée de noyaux de deutérium et de tritium par le confinement magnétique d'un plasma chaud. L'interaction entre le plasma et les parois a été étudiée en détail pour le tokamak Tore Supra. Au cours des décharges, le plasma interagit fortement avec le limiteur, formé de milliers de tuiles en composite carbone/carbone. L'érosion de ces tuiles par les flux de particules du plasma mène à la formation de co-dépôts de carbone et de deutérium qu'il est essentiel de limiter. Nous avons effectué une étude multi-échelle, principalement avec les différents outils de la microscopie électronique, sur des tuiles provenant du limiteur de Tore Supra. Une analyse des co-dépôts a permis de mettre en évidence leur topographie en forme de pointes, orientées dans une même direction quelque soit la position de la tuile sur le limiteur. L'étude de la surface de tuiles appartenant à des zones majoritairement érodées a révélé la présence d'une striation périodique de surface. Ces deux phénomènes ont été mis en relation avec la direction des flux et l'effet de la gaine faiblement magnétisée de Tore Supra a été mis en évidence. L'analyse des dépôts présents dans les interstices entre les tuiles a révélé une physique propre à ces interstices permettant la formation de dépôts en profondeur. Des nanoparticules graphitiques sphériques ont été observées, signe d'une croissance homogène locale en phase plasma. Nous avons développé des méthodes de mesure des volumes de dépôt et des volumes érodés, menant à l'établissement d'un bilan carbone et à l'évaluation de la masse de deutérium piégé, en bon accord avec les mesures in-situ réalisées dans Tore Supra. / Tokamaks are devices aiming at achieving controlled fusion of deuterium and tritium by magnetically confining a hot plasma. The interaction between the plasma and the inner walls is a crucial issue and has been studied in detail in Tore Supra. During discharges the plasma strongly interacts with limiter, designed with thousands of carbon tiles (C/C composite). The plasma particle fluxes erode the tiles, leading to co-deposition of carbon and deuterium that should be limited. We have performed a multi-scale study of tiles extracted from the Tore Supra limiter, mainly using electron microscopy. The analysis of the co-deposits has revealed a tip-shaped topography, tips being oriented in the same direction wherever the tile over the limiter. Analyses of tiles extracted from erosion-dominated zones have revealed the presence of a periodic ripple on their surfaces. Both phenomena have been related with the direction of ion fluxes and the effect of the weakly magnetized sheath of Tore Supra has been shown. Analyses of the deposits inside the gaps in-between the tiles have revealed the existence of specific processes leading to the formation of deposits deeply inside the gaps. Graphitic nano-particles have been observed, showing the existence of local homogeneous growth processes. Finally, by measuring the deposit volume and the C/C composite eroded volume we have obtained an inventory of both carbon and deuterium which is consistent with the analyses of Tore Supra in-situ measurements.

Les études portent sur les propriétés optiques de nanofils d’or individuels et de réseaux de nanofils d’or. Malgré ses avantages, comme une sensibilité moindre à l’oxydation et sa biocompatibilité, les nanofils en or ont été peu étudiés par comparaison avec les nanofils en argent ou semiconducteurs. Les études sur ces substrats ont été réalisées par spectroscopie Raman exaltée de surface (SERS). Le régime de la molécule unique est atteint, ce que j’ai démontré en utilisant deux molécules différentes de colorant, co-déposées. J’ai étudié la propagation des plasmons de surface dans les nanofils ainsi que son évolution en fonction de la longueur d’onde. Une distance de propagation de 3,8 µm a été observée, plus grande que les valeurs précédemment rapportées. Les réseaux de nanofils ont également été étudiés en combinant la réponse de deux molécules pour démêler les différents processus contribuant au signal de la diffusion Raman. Les résultats obtenus par des études en polarisation et en fonction de la longueur d’onde sur l’évolution de l’intensité du signal SERS ont été confrontés aux résultats de simulations réalisées par la méthode de l’approximation des dipôles discrets (DDA). La microscopie de champ proche optique à balayage (SNOM) a été mise en œuvre pour étudier les effets d’exaltation locale sur les réseaux de nanofils. Ces études ont été réalisées avec deux polarisations croisées et à deux longueurs d’onde différentes. L’originalité des études SNOM repose sur l’utilisation de deux modes différents d’éclairement. L’un est utilisé pour cartographier l’exaltation des champs électromagnétiques, l’autre pour étudier les effets de propagation des plasmons dans les nanofils. / We have reported the optical properties of isolated gold nanowires and of nanowire arrays. Despite the advantages gold has to offer as it is less sensitive to oxidation and as an biocompatible metal, it has been scarcely studied than silver or semiconductors nanowires. We have made surface enhanced Raman spectroscopic (SERS) studies on the isolated nanowires and nanowire arrays. Single molecule regime is attained and has been proven with the aid of two dye molecules that are co-deposited. The propagation of surface plasmons in these nanowires and their evolution with the excitation wavelength have been studied. We report a propagation distance of 3.8 µm which is longer than the values previously reported in literature. Nanowire arrays have been investigated with two dyes again to disentangle the various factors contributing to SERS. Polarization studies and the evolution of enhancement in the nanowires with the wavelength have been reported and explained with the aid of simulations obtained by the discrete dipole approximation (DDA). The scanning near field optical microscopy (SNOM) has been done to investigate the local field enhancements on the nanowire arrays. Two different polarizations and two excitation wavelengths have been used. The original idea of the technique includes the use of two illumination modes which serves two purposes. One, to map the regions of enhanced field and the other to study the propagation effects seen on the nanowire.