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.

In character animation achieving realistic deformations of the skin is a challenging task. Geometric skinning techniques, such as smooth blending or dual-quaternions, are very popular for their high performance but fail to produce convincing deformations. They look too soft compared to human skin deformation at a rigid bone joint. In addition advanced effects such as skin contacts or bulges are not taken into account. Other methods make use of physical simulation or volume control to better capture the skin behavior, yet they cannot deliver real-time feedback. We developed a novel skinning framework called implicit skinning. Our method produces visually plausible deformations in real-time by handling realistic skin contacts and bulges between limbs. Implicit skinning exploits the ability of implicit surfaces to be robustly combined as well as their efficient collision detection. By approximating the mesh by a set of implicit surfaces, we are able to guide the deformation of a mesh character. we can combine the implicit surfaces in real-time, and use the final implicit surface to adjust the position of mesh vertices at each animation step. Since collision detection is very efficient using implicit surfaces we achieve skin contacts between limbs at interactive to real-time frame rates. In this thesis we present the complete implicit skinning framework, that is, the conversion of a mesh character to implicit surfaces, the composition operators and the mesh deformation algorithm on top of the implicit surface. Two deformation algorithms are studied: a fast history dependent algorithm which acts as a post process on top of dual-quaternions skinning and a slower yet more robust history dependent algorithm. / Graduate

The various origins proposed for intercrater plains on Mercury and the Moon lead to divergent thermal, tectonic, and bombardment histories. Relative ages of geologic units and structures place tight constraints on their origin and on the planet's geologic history. Crater statistics, lunar geologic map analysis, and geologic mapping of a quarter of Mercury's surface based on plains units dated relative to crater degradation classes were used to determine relative ages. Such studies provided the basis for deducing the origin of intercrater plains and their role in terrestrial planet evolution. Mercury's extensive intercrater plains span a range of ages contemporaneous with the period of heavy bombardment. Most intercrater plains predate scarp formation and the formation of the hilly and lineated terrain. The age of the latter is identical to that of its probable progenitor, the Caloris basin impact. Post-Caloris plains--smoother in texture, less extensive, and confined to crater depressions--formed as cratering waned and scarp formation progressed. This research indicates that mercurian intercrater plains are volcanic deposits interbedded with ballistically emplaced ejecta and reworked by basin secondaries and smaller impacts. A greater proportion of ejecta may comprise lunar intercrater plains. Neither the lunar nor mercurian intercrater surface is primordial because each preserves pre-plains crateriforms. Ancient volcanism on Mercury is evidenced by widespread plains distribution, structurally controlled deposition, embayment of craters and basins, associated (but tentative) volcanic landforms, losses of small craters, and uncorrelated plains and crater coverage. The limited range of mercurian ejecta reduces the resurfacing potential relative to that of lunar craters. Crater densities are affected by intercrater plains emplacement, additions of secondaries, ancient basin impacts, and target physical properties. "One-plate" thermo-tectonic models best explain the geologic characteristics recognized in this study. Thermal expansion during core formation causes global extension and widespread volcanic extrusions; subsequent cooling and radial contraction form compressional scarps. Younger plains-forming materials issue from magma reservoirs in subsurface tensional zones tapped by impact fractures. The age and stress environment of these volcanic plains suggest a source greater than 40 km depth and a composition different from that of the intercrater plains.

Cette thèse porte sur la modélisation de l'ébullition qui joue un rôle important dans les vitessesde refroidissement des pièces, elle possède un volet numérique et un volet expérimental. Lessimulations et les expériences envisagées se situent à deux échelles. A l'échelle d'une ou quelquesbulles de vapeur, il s'agit de faire des simulations multiphasiques très précises en prenant encompte, la tension de surface, les calculs directs d'écoulement à grand nombre de Reynolds, etrendant compte du détachement et de la coalescences des bulles. Des observations expérimentalessont réalisées à la même échelle en contrôlant en surface la nucléation d'une bulle de vapeur àl'aide d'une caméra rapide. Des mesures de champs de vitesse par PIV et de température par twocolor LIF thermometry sont réalisées dans les mêmes conditions. Ceci a permit de confronter lacroissance, la dynamique et les formes des bulles observées et calculés. Les techniques numériquesles plus avancées sont utilisées : Eléments finis stabilisé VMS, level set, adaptation anisotropeet calcul intensif. Les modéles numériques proposés dans cette thèse permettent de passer àl'échelle macroscopique des pièces industrielles en considérant un film de vapeur (ou une phasede mélange liquide vapeur). L'enjeu supplémentaire étant de modéliser la turbulence induite parl'ébullition dans une approche de type CFD. / This thesis focuses on the modelling of boiling that plays an important role on the coolingand heat treatment in quenching processes, it has two components: numerical simulations andexperimental measurements. Both simulations and experiments are envisaged for two scales. Thefirst one concerns small scales: the scale of one or few bubbles. In this case, the focus is put onvery precise numerical simulations for multiphase flows taking into account the surface tension,the direct computations of flows at high Reynolds number, and on reflecting the detachmentand coalescence of bubbles. On that same scale, experimental observations are performed tocontrol, in the volume or at surface, the nucleation of a vapour bubble using a high speedcamera. Measurements of velocity fields by PIV and the temperature by PLIF are realizedunder the same conditions. This will allow us to compare the growth dynamics and shapesof bubbles observed and calculated. Advanced numerical methods are used to fulfil this task:VMS stabilized finite elements, level set, anisotropic adaptation and parallel computing. Thenumerical models proposed in this work are extended and also used to deal with macroscopicscales: at the level of industrial parts considering the vapour films (or a phase of liquid vapourmixture). The additional challenge resides in the modelling of turbulence induced by boiling ina CFD approach.

We present an optical surface in closed form that can be used to design lenses for controlling relative illumination on a target surface. The optical surface is constructed by rotation of the pedal curve to the ellipse about its minor axis. Three renditions of the surface are provided, namely as an expansion of a base surface, and as combinations of several base surfaces. Examples of the performance of the surfaces are presented for the case of a point light source. (C) 2016 Society of Photo-Optical Instrumentation Engineers (SPIE)

Résidus du disque primitif dans lequel les planètes se sont formées, les astéroïdes et les comètes fournissent des contraintes sur les processus de formation et d’évolution du système solaire. A partir des images de la mission Rosetta, l’objectif de cette thèse est de caractériser les morphologies de surface de ces petits corps, et d’en étudier les processus qui ont permis de les former et de les faire évoluer.Sur l’astéroïde (21) Lutetia, le relief est contrôlé par les impacts, formant des cratères, des nappes d’éjectas, des fractures et des boulders.Sur la comète 67P, la région Imhotep, située au niveau de l’équateur, présente des terrains lisses et des terrains consolidés très fracturés. Elle est la seule région à présenter des dizaines de structures circulaires de moins de 60 m de diamètre, probablement très anciennes (Ga), que l’on trouve associées à des couches stratifiées de quelques mètres d’épaisseur. Lors du passage au périhélie, des changements de grande envergure se sont produits dans les terrains lisses ; ils pourraient être liés aux contraintes mécaniques opérant dans le sous-sol de la comète. Un type particulier de fractures observé en surface de 67P a aussi été étudié. Ces fractures se joignent pour former des polygones 3 m en moyenne. Ces polygones résultent probablement des fortes variations de température en surface et en subsurface. Plus généralement, les observations et les travaux d’interprétation à partir des données de la mission Rosetta montrent que les morphologies de surface sur 67P sont autant dues à sa formation et à des processus endogènes qu’à des processus exogènes et évolutifs tels que la sublimation ou les contraintes thermiques. / Residuals from the accretion disk in which planets formed, asteroids and comets provide important constraints on the solar system formation and evolution processes. Based on the images from the Rosetta mission, the main objectives of this thesis are to characterize the morphologies at the surface of these small bodies and to study the processes responsible for their formation and evolution.On asteroid (21) Lutetia, the relief is controlled by impacts, forming craters, ejecta blankets, fractures and boulders.On the nucleus of comet 67P, the Imhotep region, located at the equator of the nucleus, presents smooth terrains and consolidated terrains, heavily fractured. It is the only region that shows tens of circular features less than 60 m in size, probably ancient, which we find associated with layers of several meters thick. During the passage at perihelion, major changes occurred in smooth terrains ; they may be linked to mechanical stresses acting in the nucleus subsurface. A particular type of fractures observed at the surface of 67P has also been studied in detail. These fractures join each other in polygons of roughly 3 m in size. These polygons probably result from the strong variations of temperature at the surface and subsurface. More generally, the observations and their interpretation from Rosetta data show that the morphologies at the surface of 67P can result from its formation and endogeneous processes, as well as from exogeneous and evolutionary processes such as the sublimation of ices or thermal stresses.

"The design and development of chemically modified surfaces for bioanalytical applications is presented. Chemical surface modification is demonstrated to be a method to control surface properties on the molecular level by selecting the appropriate substrate, linking chemistry, and terminal group functionality. These systems utilize spontaneous interactions between individual molecules that allow them to self-assemble into larger, supramolecular constructs with a predictable structure and a high degree of order. Applications investigated in this thesis include: surface patterning, switchable surface wettability, and biological sensor devices that combine surface based molecular recognition, electrochemical detection methods, and microfluidics. A multilayered approach to complex surface patterning is described that combines self-assembly, photolabile protecting groups, and multilayered films. A photolabile protecting group has been incorporated into molecular level films that when cleaved leaves a reactive surface site that can be further functionalized. Surface patterns are created by using a photomask and then further functionalizing the irradiated area through covalent coupling. Fluorophores were attached to the deprotected regions, providing visual evidence of surface patterning. This approach is universal to bind moieties containing free amine groups at defined regions across a surface, allowing for the development of films with complex chemical and physico-chemical properties. Systems with photoswitchable wettability were developed by fabricating multilayered films that include a photoisomerizable moiety, cis-/trans- dicarboxystilbene. When this functionality was incorporated into a multilayered film using non-covalent interactions, irradiation with light of the appropriate wavelength resulted in a conformational change that consequently changed the hydrophobicity of the substrate. Methods were investigated to increase the reversibility of the photoswitching process by creating surface space between the stilbene ligands. Utilizing mixed monolayers for spacing resulted in complete isomerization for one cycle, while the use of SAMs with photolabile groups produced surfaces that underwent isomerization for three complete cycles. A microfluidic device platform for ion sensing applications has been developed. The platform contains components to deliver small volumes of analyte to a surface based microelectrode array and measure changes in analyte concentration electrochemically in an analogous method to that used in conventional electrochemical cells. Crown ether derivatives that bind alkali metal ions have been synthesized and tested as ionophores for a multi-analyte device of this type, and the sensing platform was demonstrated to measure physiological relevant concentrations of potassium ions. Advantages of this design include: high sensitivity (uM to mM), small sample volumes (less than 0.1 mL), multi-analyte capabilities (multiple working electrodes), continuous monitoring (a flow through system), and the ability to be calibrated (the system is reusable). The self-assembled systems described here are platform technologies that can be combined and used in molecular level devices. Current and future work includes: photopatterning of gold and glass substrates for directed cell adhesion and growth, the design and synthesis of selective ion sensors for biological samples, multi-analyte detection in microfluidic devices, and incorporating optical as well as electrochemical transduction methods into sensor devices to allow for greater sensitivity and self-calibration."