All oxide heterostructure Cr2O3/TiO2-x was deposited on Al2O3(0001) single crystal via MBE. The analysis of interfacial interactions involving two metal oxides resulting in magnetic properties gave insights for using such heterostructures as potential spintronic device materials. The corundum phase epitaxial growth of TiO2-x on Al2O3 was characterized using XPS, AES, EELS, and LEED. The data obtained gives evidence of presence of two-dimensional electron gas at titania surface due to oxygen vacancies formation after deposition. On titania, the deposition of chrome in UHV results in the formation of oxidized chromia overlayer by abstraction of oxygen from the TiO2-x underlayer further increasing the number of vacancies present. In industrial R&D project, dry etching of multiple optical device components was performed using a novel angled etch prototype tool. The first set of experiments involved plasma etching of SiC thin films optimized for target application. The best-known method (BKM) worked from 300mm full wafer to 200mm product. In second experimentation, a variety of gray-tone photoresist received from customers were etched using BKM. Customer received etch rate on each gray-tone material. The third experiments compared recipe R1 to test recipe R2 on the test vehicle VDC. R2 showed faster etch rate but lower process repeatability (RMSE%). With continuous improvement of the tool and the process, two tools are operating products every day, a third prototype tool is about to be in pilot production.

An experimental study of phase transitions of long-chain n-alkanes induced by the effect of interfaces is described. ¶ The phase behaviour of long-chain n-alkanes (carbon number 14, 16, 17, 18) adsorbed at isolated mica surfaces and confined between two mica surfaces has been studied in the vicinity of and down to several degrees below the bulk melting points, Tm. Using the Surface Force Apparatus we have measured the thickness of alkane films adsorbed from vapour (0.97 [equal to or greater-than] p/p[subscript o] [equal to or greater-than] 0.997), studied capillary condensation transition, subsequent growth of capillary condensates between two surfaces, and phase transitions in both the adsorbed films and the condensates. By measuring the growth rate of the capillary condensates we have identified a transition in the lateral mobility of molecules in the adsorbed films on isolated mica surfaces. This transition to greater mobility occurs slightly above Tm for n-hexadecane, n-heptadecane and n-octadecane but several degrees below Tm for n-tetradecane, and is accompanied by a change in wetting behaviour and a measurable decrease in adsorbed film thickness for n-heptadecane and n-octadecane. Capillary condensates that form below Tm remain liquid, but may freeze if the degree of confinement is reduced by separation of the mica surfaces. An increase in the area of the liquid-vapour interface relative to that of the liquid-mica interface facilitates freezing in the case of the long-chain alkanes, which show surface freezing at the liquid-vapour interface. ¶ Although thermodynamic properties of the surface freezing transition have been rather well documented, the kinetics involved in formation of such ordered monolayers has so far received very little attention. We studied the surface tension of n-octadecane as a function of temperature in the vicinity of Tm, using the static Wilhelmy plate and the dynamic maximum bubble pressure methods. The two methods give different results on cooling paths, where nucleation of the surface ordered phase is involved, but agree on heating paths, where both methods measure properties of the equilibrium surface phase. On cooling paths, the surface of bubbles may supercool below the equilibrium surface freezing temperature. The onset of surface freezing is marked by a sharp drop in the surface tension. The transition is accompanied by an increased stability of the films resulting in longer bubble lifetimes at the liquid surface, which suggests that the mechanical properties of the surfaces change from liquid-like to solid-like. Our results suggest occurrence of supercooling of the monolayer itself.

En présence d'éléments d'alliage, l'aluminium présente d'excellentes propriétés mécaniques, obtenues grâce à un durcissement structural (alliages Al/Cu/Mg). Ces alliages constituent ainsi des matériaux largement utilisés dans le domaine de l'aéronautique. De plus, l'aluminium possède la capacité à former en présence d'oxygène un oxyde très stable qui conduit à des revêtements utilisables à hautes températures et présentant une bonne résistance à l'oxydation et à la corrosion dans un environnement agressif. Vu les enjeux économiques associés à ces propriétés, la compréhension des phénomènes à l'origine de la formation et de la microstructure des dépôts ainsi que l'influence de la présence du cuivre dans une surface d'aluminium sur l'adsorption de l'oxygène méritent d'être approfondie. Les deux axes principaux de l'étude théorique que nous présentons sont l'étude de la ségrégation du cuivre dans l'aluminium et l'étude de l'adsorption de l'oxygène atomique sur des surfaces d'alliages Al-Cu. La théorie de la fonctionnelle de la densité est actuellement la méthode ab initio la plus adaptée pour accéder aux propriétés énergétiques et électroniques de ces systèmes. Pour une concentration massique en Cu inférieure à 4%, le diagramme des phases expérimentale Al/Cu montre la formation d'une solution solide α. Une augmentation de la concentration en cuivre entraine la précipitation de cuivre sous la forme de zones de Guinier-Preston1 et 2 (GP1 et GP2) puis du premier composé déni Al2Cu (θ' métastable, puis θ stable). Nos calculs montrent que pour des phases à des concentrations en cuivre inférieures à 4%, une tendance à la formation d'une solution solide est observée en accord avec le diagramme des phases expérimentale. Nous discutons la stabilité d'alliages ordonnés Al/Cu en fonction de l'orientation de la surface, de la concentration en atomes de cuivre et de leur position par rapport à la surface. Les systèmes étudiés sont constitués d'une couche d'alliage dans un massif d'aluminium. Des atomes de cuivre sont dans un premier temps substitués à l'aluminium en surface. Cette couche est par la suite enterrée dans le massif. Les énergies de ségrégation calculées indiquent que le système est plus stable quand les couches d'alliage sont enterrées proche de la surface. La même tendance est observée pour les zones de GP1 et GP2, modélisées par des agrégats de 3 atomes de cuivre orientés selon la direction (100) dans l'aluminium (111). La substitution d'une monocouche complète de cuivre dans une surface Al(100) montre quant à elle une ségrégation du cuivre loin de la surface. L'ensemble des résultats indique clairement que les propriétés géométriques et énergétiques des systèmes Al/Cu sont nettement dominées par une tendance préférentielle du cuivre à ségréger proche de la surface Al(111). Les surfaces nues ayant été étudiés, nous nous sommes ensuite intéressés à l'adsorption de cuivre puis d'oxygène atomiques. Nous avons mis en évidence l'adsorption thermodynamiquement favorisée du cuivre en positions cfc, hcp et ponté sur une surface Al(111). L'adsorption est liée à un fort transfert électronique de la surface du matériau vers l'adsorbat. Ce comportement est encore plus fort dans le cas de l'adsorption de l'oxygène sur l'aluminium pur. En présence de cuivre, l'énergie d'adsorption de l'oxygène est fortement réduite (déstabilisation du système). Ce phénomène est d'autant plus important que le cuivre sera proche de la surface d'aluminium et donc de l'adsorbat. Hormis la répulsion électrostatique, nous n'observons néanmoins aucune interaction entre l'atome de cuivre et l'atome d'oxygène. La diminution de l'énergie d'adsorption de l'oxygène résulte essentiellement de la compétition entre les transferts électroniques vers le cuivre et l'oxygène à partir de la surface de l'aluminium. / Aluminum is often alloyed to modify some of its intrinsic properties and various treatments such as precipitation hardening are needed to improve its mechanical properties (Al/Cu/Mg alloys). The properties of these alloys are not due simply to their chemical composition but are particularly influenced by the involved phases and the alloy microstructure. Copper-aluminum alloys that have good mechanical properties are the most used alloys in the aeronautical field. Aluminum has also the capacity to form a very stable oxide. Thus, it leads to high temperature resistant coatings with good resistance to oxidation and corrosion in aggressive environments. Therefore, investigating the origins of the microstructure and the formation of the clusters as well as the influence of the copper atoms in the aluminum surface, on the oxygen adsorption is of crucial importance to comprehend these phenomena at larger scales. This study investigates theoretically in one hand, the copper segregation in aluminum and on the other hand, oxygen adsorption on Al-Cu surface alloys. This work is carried out in the framework of the density functional theory, which is at the moment the most adapted ab initio method to deal with the structural and electronic properties of these systems. According to the Al/Cu equilibrium phase diagram, at Cu atomic concentration lower than 4%, one is in presence of a solid solution α. When increasing the Cu concentration in the Al matrix, the Cu first precipitate within the bulk into Guinier-Preston1 and 2 (GP1 et GP2) zones and that later transformed to Al2Cu (metastable θ' and stable θ phases). At low copper concentration (<4%at.), we observe a tendency to the formation of a solid solution at T=0 K. We investigated surface alloys properties for varying compositions of a Cu doped Al layer in the Al (111) surface then buried in the slab. Calculated segregation energies show that the systems are more stable when the Cu doped layer is buried close to the surface. The same results are observed for first stage formation of GP zones, modelled by doping Al (100) layers with Cu clusters in a Al (111) slab. However the segregation of a full copper (100) monolayer in an Al (100) matrix shows a copper segregation deep in the bulk. Our results fit clearly into a picture of energetics and geometrical properties dominated by preferential tendency to Cu-clustering close to the Al (111) surface. Clean surfaces being fully described, we studied the adsorption of copper and oxygen atoms on clean Al (111) surface. We highlight a thermodynamically favoured adsorption of copper atoms on Al (111) surface upon fcc, hcp and bridge adsorption hollow-sites. The adsorption is related to the electronic transfer from the surface towards the adatom. The adsorption is even stronger when adsorbing oxygen on Al (111) surface. Nevertheless, in the presence of copper, the oxygen adsorption energy is weaker (destabilization of the system). The energy decrease is even more important as the copper is close to the surface, hence the adatom. Aside from the electrostatic repulsion, we observe no interaction between the copper and the oxygen atoms. The adsorption energy diminution is essentially due to the competition between the electronic transfers towards the copper and the oxygen from the aluminum surface.

Afin de convertir un maillage triangulaire en une surface spline de CAGD/CAM, cette thèse adresse l’un des problèmes les plus cruciaux du processus de conversion : extraire un “bon” maillage de contrôle quadrilatéral de la surface. Ce que nous entendons par “bon” est que les arêtes du maillage de contrôle se croisent perpendiculairement et sont alignées avec les principales directions de la courbure de la surface. Ces deux propriétés du maillage de contrôle permettent de fournir une bonne approximation de la surface avec peu de points de contrôles. D’ailleurs, ils aident considérablement à réduire des oscillations non désirées sur la surface spline finale. Pour résoudre ce problème, nous proposons un nouvel algorithme automatique, appelé paramétrisation globale périodique. L’idée fondamentale de cet algorithme est de trouver une paramétrisation qui ait un “sens d’un point de vue géométrique”, pour ce faire, elle doit être guidée par la courbure de la surface, représentée par une paire de champs de direction orthogonaux. Les iso-lignes de cette paramétrisation sont ensuite extraites pour définir un maillage de contrôle qui ait les propriétés requises. Ce maillage de contrôle, nous permet de construire une approximation en surface T-spline de la surface triangulée initiale. Nous exposons plusieurs résultats de cette conversion d’un maillage triangulée en surface spline. Les résultats montrent que, grâce aux maillages de contrôle anisotropes, les surfaces spline finales ont beaucoup moins d’oscillations que celles construites par les méthodes précédentes qui ne tiennent pas compte de l’anisotropie de la surface / Aiming at converting a triangular mesh into a CAGD/CAM spline surface, this thesis focuses on one of the most crucial problems of the conversion process, i.e. extracting a “good” quadrilateral control mesh of the surface. What we mean by good is that the edges of the control mesh should be orthogonal and aligned with the principal directions of curvature of the surface. These two properties make the control mesh optimum in an approximation point of view, and greatly help to reduce unwanted oscillations on the final spline surface built from it. To solve this problem, we propose a new automatic algorithm, called periodic global parameterization. The basic idea is to find a “geometry-meaningful” parameterization guided by a pair of orthogonal anisotropic direction fields. Then, the iso-value lines of this parameterization will be extracted to define an initial control mesh, that satisfies the two criteria of a good control mesh. With the initial control mesh, we explain how to construct a T-spline approximation of the initial triangulated surface. We show several examples of the triangular mesh to T-spline conversion. The results show that thanks to the anisotropic control meshes, the final spline surfaces generated have much less oscillations as compared to results of previous methods, that do not take into account of the anisotropy

Surface roughness exists at many length scales-from atomic dimensions to meters. At sub-micron scale, the distribution of roughness is largely dependent on the process that generates the surface through the mechanisms of material removal/addition involved and the process parameters. The focus of the research is to quantitatively characterize the evolution of sub-micron scale surface roughness in the mechanical, chemical and electrochemical material removal techniques and study the influence of roughness on the mechanical behavior of surfaces. High purity aluminum surfaces are subjected to surface dissolution techniques such as electropolishing, chemical etching and anodization. Owing to the lack of sufficient lateral resolution in conventional roughness measurement techniques and appropriate scale independent roughness characterization techniques, the effect sub-micron scale electrochemical inhomogeneities present on the surfaces have on the roughness evolution at various length scales has not been understood. In this work, the power spectral density method of roughness characterization is used to quantitatively evaluate the roughness length scales affected in the surface generation processes as a function of time. Results indicate that in the case of electropolishing, roughness is not uniformly reduced at all length scales. Further, cut-off frequencies are suggested to optimize the electropolishing process. In chemical etching, the nature of roughness produced is found to be dependent on the nature of the starting surface. The nature of surface and sub-surface structures produced in the initial stage of the anodization process, and the transition from a disordered to an ordered structure are studied. In order to study the mechanical behavior of surfaces as a function of surface roughness, a single asperity indentation is modeled using nanoindentation of micropillar produced by focused ion beam machining of aluminum surfaces. Load-displacement curves are constructed to show the transition from a single asperity deformation to bulk deformation as function of indentation depth. Additionally, indentation responses of polymer coated surfaces with varying degree of roughness that were produced by the aforementioned surface generation processes are studied. it is shown how high interface roughness gives rise to high scatter both in loading and unloading portions of the load-displacement curves. Finally, porous alumina surface generated by the anodization process discussed above is indented to simulate a multi-asperity interaction.

Dans un avenir proche, les dispositifs de détection médicaux miniaturisés en temps réels (lab-on-chip) seront au centre de la révolution des méthodes de diagnostics médicaux et d’identification des processus biologiques et cela, autant au niveau clinique qu’au niveau de la recherche. Pour y arriver, il est important de développer des chimies de surface stables et spécifiques, ce qui demande une compréhension des interactions intermoléculaires à l’interface liquide/solide. Pour bien comprendre ces interactions, il est important de développer des instruments adaptés à la mesure près de l’interface liquide/solide des différentes caractéristiques à identifier. Ce projet de recherche présente la conception, la fabrication et les expériences tests d’un capteur multimodal pour l’identification de processus biologiques à l’interface basés sur des technologies de résonance des plasmons de surface (SPR) et de microcalorimérie. Ces deux technologies mises ensemble vont permettre d’effectuer des mesures de la cinétique des interactions ainsi que des caractéristiques thermodynamiques. En premier lieu, les caractéristiques d’une interaction intermoléculaire à l’interface d’une réaction d’hybridation d’ADN furent définies afin d’en déduire un cahier des charges pour les transducteurs. Suite à cela, la conception des transducteurs microcalorimétrique et SPR furent réalisés en tenant compte des contraintes de chacun des transducteurs. Suite à la conception théorique des différentes parties du capteur, un procédé de fabrication compatible avec les méthodes de fabrication standard de la microélectronique fut défini et testé. Afin de s’assurer de la fonctionnalité des dispositifs ainsi fabriqués, des tests de fonctionnalisation de surface furent appliqués sur les échantillons afin de tester la compatibilité du procédé de fonctionnalisation avec les méthodes de fabrication et avec une chimie de surface type. Pour terminer, un système de mélange actif fut testé et caractérisé avec le dispositif de microcalorimétrie afin de s’assurer qu’il était possible de mélanger les fluides avec les produits biologiques pour s’assurer de la qualité de la réaction de surface. Le système développé pourra être utilisé pour effectuer la mesure d’hybridation d’ADN à l’interface. Le système intègre deux modalités permettant la caractérisation en temps réel des interactions intermoléculaires à l’interface liquide/solide. Ce type de système permet la mesure de la cinétique de différents modèles biologiques tels que les puces à sucre encore certains récepteurs cellulaires ou la mesure de conformation moléculaire à l’interface. Des mesures d’oxydation du glucose catalysée par la glucose oxydase sont montrées. / To begin with, the characteristics of a DNA hybridization intermolecular interaction at the interface were defined in order to deduce the specifications for our transducers. Following this, the SPR and microcalorimetric transducer will be design by taking into account the constraints of each one. Following the theoretical design of the sensor, a manufacturing process compatible with standard methods of microelectronics manufacturing was tested and identified. To ensure the functionality of the devices, a test of surface functionalization on the sensor was applied to test the compatibility of the manufacturing process with the surface functionalization methods. Finally, a system of active mixing was tested and characterized with a microcalorimetric device to ensure it was possible to mix fluids with organic products to be sure of the quality of the surface reaction. The system developed can be used to mesure DNA hybridization at the interface. This system incorporates two modalities for real-time characterization of intermolecular interactions near the solid/liquid interface. This type of system allows the kinetic measurement of different biological models such as cellular receptors or it is possible to have some molecular measure conformation near the interface. Oxidation of glucose with the enzyme glucose oxidase was shown to present the possibility to measure a biological interaction.

A firm knowledge about the interaction between the metal surface and adsorbed molecules is imperative for formulating procedures to synthesize nanoparticles (NPs) with predetermined shape and size. The ligand‐metal interaction during NP formation can be mimicked on an electrode surface by electrosorbing ligand molecules on a charged metal surface. Electrochemical methods can provide an ideal platform to study the adsorption behaviour of molecules at the solid‐liquid interface. In addition to classical electrochemical techniques, the combination of spectroscopy with electrochemical methods amplifies mechanistic insights about the surface adsorption processes. The adsorption behaviour of pyridine and one of its derivatives, 4‐dimethylamino pyridine (DMAP) have been well studied due to their potential application in nanoparticle synthesis. However, prior to this work, there has been very limited and conflicting literature available about the adsorption of of pyridine derivatives analogous to DMAP. Among the pyridine derivatives that were studied, some reports indicate that, other than DMAP, only 4‐methoxy pyridine (MOP) can stabilize gold nanoparticles. However, very little is known about the possible differences in the adsorption energy and general behaviour of MOP compared to DMAP. Resolving this knowledge gap is imperative to resolving the conflicting information about pyridine‐based stabilizers for metal nanoparticle applications. The adsorption behaviour of MOP on different crystallographic Au surfaces as a function of pH and surface potential has been investigated in this project. These studied were carried out using classical electrochemical methods including chronocoulometry and differential capacity, as well as modern spectroscopic techniques like Surface Enhanced Infrared Absorption Spectroscopy (SEIRAS). The thermodynamic parameters obtained from electrochemical data shows that adsorption features of MOP is similar to that of DMAP. However, there is a significant difference in the adsorption strength of MOP and DMAP at positive potentials. The SEIRAS data provides much more detailed information about the potential depended orientation of MOP on polycrystalline Au. Cumulative analysis of electrochemical and spectroscopic data provides strong evidence that MOP can stabilize Au(111) facets over wide pH ranges. Moreover, this work provides convincing evidence that the basic nature of substituted pyridine alters the metal to ligand adsorption strength.

The purpose of this study was to develop a composite manufacturing process that would be able to deliver Class A surface finished products in the context of mould manufacturing methods. The problem required solving was to overcome the time needed to prepare Class A surfaces, by developing a composite manufacturing process that will deliver Class A surface finished products straight from the mould. The process was aimed at the entire development process, from mould and plug design up to the finished product. A literature study and a factory mould survey were conducted with a view to obtain the necessary insights into surface finishing and composite manufacturing. These surveys were followed by seven constructional tests which determined the most appropriate solutions for the proposed manufacturing processes. Test 1 was used to determine a quality finish standard for composites from the sanding grits used to finished composite surfaces versus surface roughness values used in other industries. The standard determined that a P800 finish has a roughness between 0.200 and 0.150 um and constitutes a Class A3 finish. P1000 to P1200 have a roughness between 0.150 um to 0.100 um and constitutes a Class A2 finish. Finally a P2000 and higher have a roughness of 0.100 um and lower and constitutes Class A1 surface finish. After the standard was set, the tests for finishing of the moulds, plugs and parts commenced. Test 2 was conducted on the CNC manufacturing of plugs out of Nuceron651 tooling board. Tool path parameters were varied in a matrix. The samples with the best surface finish value were cut with a step-over of 0.5 and feed of 800 mm/min. These parameters were found to be the most influential. Test 2 and 4 revealed that the plug surface finishing should commence with conventional 2K paint finishing, with a possibility of acrylic split surface. This process produced projected mould surfaces between 0.150 um and 0.200 um, which can be categorised as Class A-3. Test 5 and 6 determined methods for improving the mould surface quality and durability. It was established that the tooling gelcoat should be applied whilst being heated and backed with at least two layers of glass veil and a steady increase of GSM of structural glass fibres to prevent print-through. Test 3 determined that the mould corners could be strengthened with rovings pressed into the corner. It was also established that the moulds surfaces will require finishing after demoulding. The final moulds were manufactured from a fibreglass composite structure with tooling gelcoat surface. A number of guidelines and a set process were developed in order to produce moulds with a surface finish of average 0.9 um, equivalent to Class A1. Release agents were tested in Test 7, and the Loctite Frekote 770-NC release system was deemed appropriate for use with In Mould Coating (IMC) of 2K Paint. These elements were all synthesised into plug, mould and part manufacturing processes. The proposed processes were validated by the manufacturing of a JS instrument panel, which delivered a Class A2, 0.175 um, finish with IMC of 2K paint. With only a minor sanding of P3000 grit and polishing, the part was made into a Class A1 surface, measured at 0.63 um. The study proved that it is possible to produce Class A finished part with IMC. This method can provide a solution aimed at the elimination of P600 and lower finishing of composite parts manufactured with IMC. / MIng (Mechanical Engineering), North-West University, Potchefstroom Campus, 2014

The purpose of this study was to develop a composite manufacturing process that would be able to deliver Class A surface finished products in the context of mould manufacturing methods. The problem required solving was to overcome the time needed to prepare Class A surfaces, by developing a composite manufacturing process that will deliver Class A surface finished products straight from the mould. The process was aimed at the entire development process, from mould and plug design up to the finished product. A literature study and a factory mould survey were conducted with a view to obtain the necessary insights into surface finishing and composite manufacturing. These surveys were followed by seven constructional tests which determined the most appropriate solutions for the proposed manufacturing processes. Test 1 was used to determine a quality finish standard for composites from the sanding grits used to finished composite surfaces versus surface roughness values used in other industries. The standard determined that a P800 finish has a roughness between 0.200 and 0.150 um and constitutes a Class A3 finish. P1000 to P1200 have a roughness between 0.150 um to 0.100 um and constitutes a Class A2 finish. Finally a P2000 and higher have a roughness of 0.100 um and lower and constitutes Class A1 surface finish. After the standard was set, the tests for finishing of the moulds, plugs and parts commenced. Test 2 was conducted on the CNC manufacturing of plugs out of Nuceron651 tooling board. Tool path parameters were varied in a matrix. The samples with the best surface finish value were cut with a step-over of 0.5 and feed of 800 mm/min. These parameters were found to be the most influential. Test 2 and 4 revealed that the plug surface finishing should commence with conventional 2K paint finishing, with a possibility of acrylic split surface. This process produced projected mould surfaces between 0.150 um and 0.200 um, which can be categorised as Class A-3. Test 5 and 6 determined methods for improving the mould surface quality and durability. It was established that the tooling gelcoat should be applied whilst being heated and backed with at least two layers of glass veil and a steady increase of GSM of structural glass fibres to prevent print-through. Test 3 determined that the mould corners could be strengthened with rovings pressed into the corner. It was also established that the moulds surfaces will require finishing after demoulding. The final moulds were manufactured from a fibreglass composite structure with tooling gelcoat surface. A number of guidelines and a set process were developed in order to produce moulds with a surface finish of average 0.9 um, equivalent to Class A1. Release agents were tested in Test 7, and the Loctite Frekote 770-NC release system was deemed appropriate for use with In Mould Coating (IMC) of 2K Paint. These elements were all synthesised into plug, mould and part manufacturing processes. The proposed processes were validated by the manufacturing of a JS instrument panel, which delivered a Class A2, 0.175 um, finish with IMC of 2K paint. With only a minor sanding of P3000 grit and polishing, the part was made into a Class A1 surface, measured at 0.63 um. The study proved that it is possible to produce Class A finished part with IMC. This method can provide a solution aimed at the elimination of P600 and lower finishing of composite parts manufactured with IMC. / MIng (Mechanical Engineering), North-West University, Potchefstroom Campus, 2014

Surface enhanced Raman scattering (SERS) is a powerful means for obtaining vibrational data from the metal/electrolyte or metal/gas interfacial environment. However, SERS is only observed for a limited number of metal surfaces under certain experimental conditions. Before this method can become a universal tool, the enhancement mechanism(s) must be understood. The results reported in this dissertation assess both electronic and chemical contributions to the SERS mechanism. The electronic properties of the metal are altered by systematic deposition of Pb or Cu onto a substrate that supports intense SERS, Ag. The chemical nature of the interface is altered with different probe molecules. The effect of Pb deposition on the SERS enhancing ability of Ag electrodes has previously been investigated with strongly adsorbed probe molecules. The behavior of cyanide species in the presence of Pb⁺² is complicated by the necessity of maintaining low solution pH to prevent Pb(OH)₂ precipitation; thus, the predominant solution species is HCN. Although previous reports state that no SERS can be detected from cyanide-containing solutions below pH 6, intense SERS signals can be obtained at pH 2 if sufficiently positive electrode potentials are maintained. The two unresolved SERS bands observed in acidic solutions are attributed to HCN which interacts with the Ag surface in end-on and side-on configurations. The predominant effect of Pb deposition on HCN SERS is HCN displacement. Enhancement due to charge transfer processes is not significant, while electromagnetic effects dictate the residual SERS intensity remaining after the initial HCN displacement. The supporting electrolyte anion affects the rate of change of the potential dependent C≡N stretch in basic CN⁻ media. A correlation between the rate of frequency change and anion charge/radius ratio was observed at potentials near and slightly negative of the Ag potential of zero charge in basic CN⁻ media. These results demonstrate the extraordinary sensitivity of SERS to interfacial conditions. The contributions from chemical and electromagnetic enhancement are further assessed by following excitation wavelength dependence of the SERS intensity of pyridine and Cl⁻ as a function of Cu coverage. Contributions from both are observed, but chemical enhancement is less evident for Cu than for Pb deposition. This is related to the smaller change in work function that occurs as a consequence of Cu versus Pb deposition on Ag surfaces.