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INTRODUCTION AND AIM Black South Africans are experiencing an increase in the prevalence of cardiovascular disease (CVD). Fibrinogen functionality, including total and gamma prime (y’) fibrinogen concentration, as well as fibrin network structure, play an important role in CVD development and events. Several genetic and environmental factors influence fibrinogen functionality, and in turn, known CVD risk factors associated with total and y’ fibrinogen concentration have also been associated with altered fibrin clot structure. However, the main body of evidence regarding the role of fibrinogen functionality in CVD is based on studies conducted in white ethnicities and/or in vitro. The main aim of this study was, therefore, to determine the relationship between fibrinogen functionality and CVD in black South Africans in a plasma setting. Since there is greater genetic diversity in Africans than in non-black ethnicities, it was also our objective to investigate the influence of genetic polymorphisms in determining fibrinogen synthesis and plasma clot properties, and to determine possible gene-environment interactions altering clot properties. PARTICIPANTS AND METHODS The South African arm of the Prospective Urban and Rural Epidemiology (PURE) study included 2010 apparently healthy black men and women between the ages of 35 and 65 years, residing in rural or urban settlements. Blood samples were collected from the participants during a 12-week period in 2005. The following variables were analysed: total and y’ fibrinogen concentration, CVD risk factors and genetic polymorphisms in the fibrinogen and Factor XIII genes as well as turbidimetric analysis of clot formation and lysis (expressed as clot lysis time (CLT)). RESULTS Increased plasma levels of both total (largest contribution of 33%) and y’ fibrinogen were associated with increased fibre diameter while y’/total fibrinogen ratio had the opposite effect. The rate of lateral aggregation of fibrin fibres (slope) increased with an increase in total fibrinogen concentration, but not fibrinogen y’. Increasing fibrinogen y’ concentration was associated with longer CLTs and was the largest contributor to its variance (12%). Increased total and y’ fibrinogen were significantly associated with increased waist circumference, body mass index, C-reactive protein (CRP), glycosylated haemoglobin, metabolic syndrome (MetS) and low high-density lipoprotein (HDL) cholesterol levels. Furthermore, the association of fibrinogen y’ with these CVD risk factors was independent of total fibrinogen levels. C-reactive protein was the largest contributor to variance in fibrinogen y’ levels and y’/total fibrinogen ratio (apart from total fibrinogen). We observed significant associations between single nucleotide polymorphisms (SNPs) at rs1049636 and rs2070011 loci and increased total and y’ fibrinogen levels, respectively. Only SNP rs1800787 was associated with clot properties (increased maximum absorbance). Significant gene-environment interactions were observed between SNPs rs2227385, rs1800787, rs1800788, rs4220 and rs5985 and total and/or y’ fibrinogen levels in determining clot properties. The CVD risk factors age, MetS, CRP, HDL-cholesterol and homocysteine associated significantly with clot properties, independent of total and/or y’ fibrinogen plasma concentration. CONCLUSION The results of this thesis provide several novel insights relevant to this research field. Plasma y’ fibrinogen concentration and y’ ratio were found to be associated with altered clot properties in a plasma setting, and are also influenced by CVD risk factors other than fibrinogen. The associations between SNPs, total and y’ fibrinogen and clot properties differ somewhat from evidence reported in white populations. Significant gene-environment interactions between SNPs and total and y’ fibrinogen in determining clot properties existed and had opposing effects, i.e. both prothrombotic and antithrombotic, suggesting that the influence of genetic factors on fibrinogen should focus not only on concentration, but also on functionality. Cardiovascular disease risk factors also influence clot properties in vivo, through mechanisms independent of total and/or y’ fibrinogen concentration. / PhD (Nutrition), North-West University, Potchefstroom Campusm, 2015

INTRODUCTION AND AIM Black South Africans are experiencing an increase in the prevalence of cardiovascular disease (CVD). Fibrinogen functionality, including total and gamma prime (y’) fibrinogen concentration, as well as fibrin network structure, play an important role in CVD development and events. Several genetic and environmental factors influence fibrinogen functionality, and in turn, known CVD risk factors associated with total and y’ fibrinogen concentration have also been associated with altered fibrin clot structure. However, the main body of evidence regarding the role of fibrinogen functionality in CVD is based on studies conducted in white ethnicities and/or in vitro. The main aim of this study was, therefore, to determine the relationship between fibrinogen functionality and CVD in black South Africans in a plasma setting. Since there is greater genetic diversity in Africans than in non-black ethnicities, it was also our objective to investigate the influence of genetic polymorphisms in determining fibrinogen synthesis and plasma clot properties, and to determine possible gene-environment interactions altering clot properties. PARTICIPANTS AND METHODS The South African arm of the Prospective Urban and Rural Epidemiology (PURE) study included 2010 apparently healthy black men and women between the ages of 35 and 65 years, residing in rural or urban settlements. Blood samples were collected from the participants during a 12-week period in 2005. The following variables were analysed: total and y’ fibrinogen concentration, CVD risk factors and genetic polymorphisms in the fibrinogen and Factor XIII genes as well as turbidimetric analysis of clot formation and lysis (expressed as clot lysis time (CLT)). RESULTS Increased plasma levels of both total (largest contribution of 33%) and y’ fibrinogen were associated with increased fibre diameter while y’/total fibrinogen ratio had the opposite effect. The rate of lateral aggregation of fibrin fibres (slope) increased with an increase in total fibrinogen concentration, but not fibrinogen y’. Increasing fibrinogen y’ concentration was associated with longer CLTs and was the largest contributor to its variance (12%). Increased total and y’ fibrinogen were significantly associated with increased waist circumference, body mass index, C-reactive protein (CRP), glycosylated haemoglobin, metabolic syndrome (MetS) and low high-density lipoprotein (HDL) cholesterol levels. Furthermore, the association of fibrinogen y’ with these CVD risk factors was independent of total fibrinogen levels. C-reactive protein was the largest contributor to variance in fibrinogen y’ levels and y’/total fibrinogen ratio (apart from total fibrinogen). We observed significant associations between single nucleotide polymorphisms (SNPs) at rs1049636 and rs2070011 loci and increased total and y’ fibrinogen levels, respectively. Only SNP rs1800787 was associated with clot properties (increased maximum absorbance). Significant gene-environment interactions were observed between SNPs rs2227385, rs1800787, rs1800788, rs4220 and rs5985 and total and/or y’ fibrinogen levels in determining clot properties. The CVD risk factors age, MetS, CRP, HDL-cholesterol and homocysteine associated significantly with clot properties, independent of total and/or y’ fibrinogen plasma concentration. CONCLUSION The results of this thesis provide several novel insights relevant to this research field. Plasma y’ fibrinogen concentration and y’ ratio were found to be associated with altered clot properties in a plasma setting, and are also influenced by CVD risk factors other than fibrinogen. The associations between SNPs, total and y’ fibrinogen and clot properties differ somewhat from evidence reported in white populations. Significant gene-environment interactions between SNPs and total and y’ fibrinogen in determining clot properties existed and had opposing effects, i.e. both prothrombotic and antithrombotic, suggesting that the influence of genetic factors on fibrinogen should focus not only on concentration, but also on functionality. Cardiovascular disease risk factors also influence clot properties in vivo, through mechanisms independent of total and/or y’ fibrinogen concentration. / PhD (Nutrition), North-West University, Potchefstroom Campusm, 2015

L’augmentation du rendement énergétique des cuves est un des objectifs principaux de la recherche sur l’électrolyse de l’alumine. Les objectifs de la thèse sont d’étudier les propriétés des dépôts, leurs facteurs de formation et leur effet sur la dégradation du bloc cathodique, notamment la chute de voltage cathodique (CVD). Une première phase des travaux a permis le développement d’une méthode de caractérisation des dépôts par le calcul de l’amorphe, l’estimation de l’alumine totale par un bilan sur l’oxygène LECO et une quantification plus précise des espèces contenant du calcium par mesure fluorescence X (XRF). L’étude d’échantillons bloc cathodique/dépôt par microscopie à balayage couplée avec la spectroscopie de la dispersion des rayons X (MEB-EDX) a aussi amené une meilleure compréhension de l’épaisseur de la couche de carbure à l’interface et de la taille des particules d’alumine dans la matrice de dépôt. Le développement d’un banc d’essai a permis de mesurer la CVD et de simuler les conditions d’électrolyse d’un bloc industriel en contrôlant l’alimentation alumine d’un côté et le refroidissement de l’autre côté. Une analyse statistique préliminaire a aidé à discerner des tendances dans la composition chimique des dépôts ainsi que des zones de dépôt précises. Des calculs thermodynamiques ont été utilisés pour obtenir la température de précipitation de la cryolite et de l’alumine et ainsi estimer la concentration solide/liquide dans les dépôts à température d’opération. Ces données ont ensuite permis l’estimation des propriétés de densité et de conductivité électrique des dépôts. Un bref exposé théorique de la formation des carbures et des oxycarbures a présenté le lien entre les travaux précédants sur l’imagerie XPS et l’effet des dépôts sur la dégradation du bloc cathodique. Plusieurs phénomènes peuvent expliquer la formation de dépôt au fond de la cuve. La dissolution incomplète de l’alumine d’alimentation et la chute du matériel de couverture d’anode amènent une fraction significative de dépôt en dessous de la nappe d’aluminium jusqu’à la surface du bloc cathodique. L’importance de l’un ou l’autre des phénomènes peut être expliquée par les propriétés de l’alumine d’alimentation, le design et l’opération de la cuve. Une fois passé l’interface aluminium/bain, le dépôt peut s’accumuler en dessous des points d’alimentation, le long du couloir central entre les anodes ou s’étendre sur l’ensemble de la surface du bloc cathodique. L’étude de quatre cuves de deux différentes technologies a montré qu’il existe une corrélation entre la formation d’un mince film, sa sursaturation en alumine, le taux de dissolution partielle de l’alumine d’alimentation, la longueur du pied de talus et la CVD. En plus de la sursaturation en alumine, le mince film conduit à l’épaississement de la couche de carbure ce qui amène une hausse de la CVD. Des expériences laboratoires ont démontré que la dissolution partielle de l’alumine produit des dépôts d’une concentration massique d’alumine en deçà de 30 % et que ces dépôts riches en alumine peuvent interagir avec le pied de talus pour former un « dépôt » liquide qui remonte dans le bain électrolytique. Les résultats laboratoires ont aussi confirmé la corrélation entre l’épaisseur du dépôt et de la couche de carbure. L’effet de la résistivité du film mince sur l’ensemble de la surface du bloc cathodique et de la longueur du pied de talus sur la CVD a été évalué à l’aide d’un modèle purement électrique. Trois types de films minces ayant une résistivité différente ont été modélisés selon des observations de composition chimique et de morphologie précédentes. Les données du modèle correspondent aux données de CVD mesurées dans des cuves industrielles, et ce, pour deux types de technologies. Le modèle montre que l’effet combiné entre le pied de talus et la présence d’un mince film résistif amène une hausse significative de la densité de courant au centre de la cuve. Ce résultat pourrait conduire à une conclusion différente sur l’effet de la présence de dépôt au centre sur la CVD. Des expériences laboratoires ont montré que la simulation d’un pied de talus par l’ajout d’une plaque d’alumine produit une hausse de la CVD mesurable. La formation d’un dépôt épais produit une hausse encore plus grande de la CVD. Toutefois, des efforts demeurent pour augmenter la précision de la mesure afin d’évaluer l’impact d’un mince film sur la CVD. L’étude d’une deuxième technologie a démontré un enrichissement du pied de talus en alumine ainsi qu’une corrélation entre la composition des dépôts au centre de la cuve et du pied de talus. Une étude approfondie des mouvements MHD supporte aussi l’existence d’une interaction entre dépôt centre et pied de talus. Il semblerait toutefois que le transport de matière net soit du centre de la cuve vers le pied de talus. L’étude de la densité des dépôts de pied de talus par tranche verticale a montré un phénomène de cristallisation des particules solides par le bas de l’échantillon ainsi que la formation d’un cœur liquide et moins dense que le reste de l’échantillon.

CVD diamond possesses certain attractive electrochemical properties inter alia low background current, broad potential window, chemical inertness and resistance to electrocorrosion and fouling. As a consequence its use in various areas of electrochemistry, such as electrochemical sensing, wastewater treatment and electrocatalysis is being explored. Unfortunately, alongside these attractive features, bare CVD diamond electrodes, in common with all other electrode materials, cannot be effectively applied in all electrochemical systems of interest, since for example it may not display useful electrochemical activity for the redox process of interest. In these circumstances it may be possible to modify the electrode by addition of other chemical species to the surface, to introduce the relevant activity. One of the main aims of this thesis was therefore to investigate the properties of certain chemical modifications to the diamond electrode surface. A second aim was also to explore for the first time the use of a practically useful form of single crystal diamond, so-called heteroepitaxial diamond, in electrochemistry. The diamond electrodes used were boron-doped material grown by chemical vapour deposition. A range of electrochemical methods, including especially cyclic voltammetry, square-wave voltammetry, impedance spectroscopy and scanning electrochemical microscopy, were used to characterise electrode properties. Other physical methods employed included scanning electron and atomic force microscopy, X-ray photoelectron spectroscopy and dynamic light scattering techniques. The electrochemical properties of heteroepitaxial single crystal diamond were explored and compared to polycrystalline counterparts. The single crystal diamond electrode was found to show superior properties in terms of wide potential window, low background current and homogeneous activity across the electrode surface, coupled with resistance to fouling. Heterogenous electron transfer rate constants were found to be lower than normally found on polycrystalline diamond; this was attributed to reduced density of states and absence of functional groups. An electrochemical route to the preparation of diamond electrodes, modified by PrOx@Pt core-shell particles was demonstrated. It was observed that these electrode modifiers were far less susceptible to poisoning than bare Pt nanoparticles when used in the electrochemical oxidation of methanol. It was also shown that diamond electrodes with these core-shell particles deposited on them, displayed useful activity for the electrochemical oxidation of nitric oxide. The presence of the PrOx layer was shown to impart useful selectivity against the oxidation of interfering compounds such as nitrite and ascorbic acid, without the loss of sensitivity which normally occurs if nafion coatings are used instead. Basic electrochemical characterisation of the PrOx coating showed that the layer was chemically active and did not serve as a simple blocking layer when deposited on the electrode. The activity of Pt modified diamond electrodes for the oxidation of nitrite species was also studied. It was also shown that the addition of carbon black to a diamond electrode resulted in much enhanced electrochemical properties in the detection of riboflavin.

We report approaches to grow ultrathin Ru films for application as a seed layer and Cu diffusion barrier. For chemical vapor deposition (CVD) with Ru3(CO)12 we show the role surface hydroxyl groups have in nucleating the Ru islands that grow into a continuous film in a Volmer-Weber process, and how the nucleation density can be increased by applying a CO or NH3 overpressure. Thinner continuous films evolve in the presence of a CO overpressure. We report an optimun ammonia overpressure for Ru nucleation and that leads to deposition of smoother Ru thin films. Finally, we report a comparison of amorphous Ru films that are alloyed with P or B and demonstrate 3-nm thick amorphous Ru(B) films function as a Cu diffusion barrier.

The objective of this thesis is to develop an easy-to-use and computationally economical numerical tool to investigate the flow field in the Pulsed Pressure Chemical Vapour Deposition (PP-CVD) reactor. The PP-CVD process is a novel thin film deposition technique with some advantages over traditional CVD methods. The numerical modelling of the PP-CVD flow field is carried out using the Quiet Direct Simulation (QDS) method, which is a flux-based kinetic-theory approach. Two approaches are considered for the flux reconstruction, which are the true directional manner and the directional splitting method. Both the true directional and the directional decoupled QDS codes are validated against various numerical methods which include EFM, direct simulation, Riemann solver and the Godunov method. Both two dimensional and axisymmetric test problems are considered. Simulations are conducted to investigate the PP-CVD reactor flow field at 1 Pa and 1 kPa reactor base pressures. A droplet flash evaporation model is presented to model the evaporation and transport of the liquid droplets injected. The solution of the droplet flash evaporation model is used as the inlet conditions for the QDS gas phase solver. The droplet model is found to be able to provide pressure rise in the reactor at the predicted rate. A series of parametric studies are conducted for the PP-CVD process. The numerical study confirms the hypothesis that the flow field uniformity is insensitive to the reactor geometry. However, a sufficient distance from the injection inlet is required to allow the injected precursor solution to diffuse uniformly before reaching the substrate. It is also recommended that placement of the substrate at the reactor’s centre axis should be avoided.

Conductive polymers, since from their discovery, have become a prominent area of research and found many useful applications in all fields of our daily life. Examples are light emitting diodes, heat generation, chemical sensors and electro-active membranes. Polymer coated textile substrates give flexible and lightweight materials. One well utilized and thoroughly explored conductive polymer is poly(3,4-ethylenedioxythiophene) also known as PEDOT. Although there are different ways to produce PEDOT one of the most common is the VPP technique. The typical procedure when using VPP is to introduce the monomer vapor to an oxidant coated substrate so that it polymerizes on the surface of the substrate. Throughout this study, the VPP technique has been used to produce PEDOT on different textile fibers. Aim was first of all optimizing the process gaining low electric resistance, i. e. high conductivity, of produced coated fibers but also multilayer coatings of fibers. Outcome indicates some parameters not having a clear influence over the results while others had a more distinct impact. A noteworthy result was obtained by coating a substrate, namely lyocell fiber, multiple times with layers deposited directly on each other. This decreased the resistance from 5.1 (± 1.6) kΩ/10 cm to 1.0 (± 0.1) kΩ/10 cm, for one layer and multiple layers respectively. Adding 15 wt. % of the copolymer PEG-PPG-PEG to the oxidant solution decreased the resistance from 6.8 (± 1.2) kΩ/10 cm to 3.9 (± 0.8) kΩ/10 cm. Final conclusion is that among the ways, to improve conductivity for PEDOT coated fibers, applied in this study are best results obtained by multi-layer coating.

In the course of the PhD thesis large area homogeneous strictly monolayer graphene films were successfully synthesized with chemical vapor deposition over both Cu and Si (with surface oxide) substrates. These synthetic graphene films were characterized with thorough microscopic and spectrometric tools and also in terms of electrical device performance. Graphene growth with a simple chemo thermal route was also explored for understanding the growth mechanisms. The formation of homogeneous graphene film over Cu requires a clean substrate. For this reason, a study has been conducted to determine the extent to which various pre-treatments may be used to clean the substrate. Four type of pre-treatments on Cu substrates are investigated, including wiping with organic solvents, etching with ferric chloride solution, annealing in air for oxidation, and air annealing with post hydrogen reduction. Of all the pretreatments, air oxidation with post hydrogen annealing is found to be most efficient at cleaning surface contaminants and thus allowing for the formation of large area homogeneous strictly monolayer graphene film over Cu substrate. Chemical vapor deposition is the most generally used method for graphene mass production and integration. There is also interest in growing graphene directly from organic molecular adsorbents on a substrate. Few studies exist. These procedures require multiple step reactions, and the graphene quality is limited due to small grain sizes. Therefore, a significantly simple route has been demonstrated. This involves organic solvent molecules adsorbed on a Cu surface, which is then annealed in a hydrogen atmosphere in order to ensure direct formation of graphene on a clean Cu substrate. The influence of temperature, pressure and gas flow rate on the one-step chemo thermal synthesis route has been investigated systematically. The temperature-dependent study provides an insight into the growth kinetics, and supplies thermodynamic information such as the activation energy, Ea, for graphene synthesis from acetone, isopropanol and ethanol. Also, these studies highlight the role of hydrogen radicals for graphene formation. In addition, an improved understanding of the role of hydrogen is also provided in terms of graphene formation from adsorbed organic solvents (e.g., in comparison to conventional thermal chemical vapor deposition). Graphene synthesis with chemical vapor deposition directly over Si wafer with surface oxide (Si/SiOx ) has proven challenging in terms of large area and uniform layer number. The direct growth of graphene over Si/SiO x substrate becomes attractive because it is free of an undesirable transfer procedure, necessity for synthesis over metal substrate, which causes breakage, contamination and time consumption. To obtain homogeneous graphene growth, a local equilibrium chemical environment has been established with a facile confinement CVD approach, inwhich two Si wafers with their oxide faces in contact to form uniform monolayer graphene. A thorough examination of the material reveals it comprises facetted grains despite initially nucleating as round islands. Upon clustering these grains facet to minimize their energy, which leads to faceting in polygonal forms because the system tends to ideally form hexagons (the lowest energy form). This is much like the hexagonal cells in a beehive honeycomb which require the minimum wax. This process also results in a near minimal total grain boundary length per unit area. This fact, along with the high quality of the resultant graphene is reflected in its electrical performance which is highly comparable with graphene formed over other substrates, including Cu. In addition the graphene growth is self-terminating, which enables the wide parameter window for easy control. This chemical vapor deposition approach is easily scalable and will make graphene formation directly on Si wafers competitive against that from metal substrates which suffer from transfer. Moreover, this growth path shall be applicable for direct synthesis of other two dimensional materials and their Van der Waals hetero-structures. / Im Zuge dieser Doktorarbeit wurden großflächige und homogene Graphen-Monolagen mittels chemischer Gasphasenabscheidung auf Kupfer- (Cu) und Silizium-(Si) Substraten erfolgreich synthetisiert. Solche monolagigen Graphenschichten wurden mithilfe mikroskopischer und spektrometrischer Methoden gründlich charakterisiert. Außerdem wurde der Wachstumsmechanismus von Graphen anhand eines chemo-thermischen Verfahrens untersucht. Die Bildung von homogenen Graphenschichten auf Cu erfordert eine sehr saubere Substratoberfläche, weshalb verschiedene Substratvorbehandlungen und dessen Einfluss auf die Substratoberfläche angestellt wurden. Vier Vorbehandlungsarten von Cu-Substraten wurden untersucht: Abwischen mit organischen Lösungsmitteln, Atzen mit Eisen-(III)-Chloridlösung, Wärmebehandlung an Luft zur Erzeugung von Cu-Oxiden und Wärmebehandlung an Luft mit anschließender Wasserstoffreduktion. Von diesen Vorbehandlungen ist die zuletzt genannte Methode für die anschließende Abscheidung einer großflächigen Graphen-Mono-lage am effektivsten. Die chemische Gasphasenabscheidung ist die am meisten verwendete Methode zur Massenproduktion von Graphen. Es besteht aber auch Interesse an alternativen Methoden, die Graphen direkt aus organischen, auf einem Substrat adsorbierten Molekülen, synthetisieren konnen. Jedoch gibt es derzeit nur wenige Studien zu derartigen alternativen Methoden. Solche Prozessrouten erfordern mehrstufige Reaktionen, welche wiederrum die Qualität der erzeugten Graphenschicht limitieren, da nur kleine Korngrößen erreicht werden konnen. Daher wurde in dieser Arbeit ein deutlich einfacherer Weg entwickelt. Es handelt sich dabei um ein Verfahren, bei dem auf einer Cu-Substratoberfläche adsorbierte, organische Lösungsmittelmoleküle in einer Wasserstoffatmosphäre geglüht werden, um eine direkte Bildung von Graphen auf einem sauberen Cu-Substrat zu gewahrleisten.Der Einfluss von Temperatur, Druck und Gasfluss auf diesen einstufigen chemothermischen Syntheseweg wurde systematisch untersucht. Die temperaturabhängigen Untersuchungen liefern einen Einblick in die Wachstumskinetik und thermodynamische Größen, wie zum Beispiel die Aktivierungsenergie Ea, für die Synthese von Graphen aus Aceton, Isopropanol oder Ethanol. Diese Studien untersuchen außerdem die Rolle von Wasserstoffradikalen auf die Graphensynthese. Weiterhin wurde ein verbessertes Verständnis der Rolle von Wasserstoff auf die Graphen-synthese aus adsorbierten, organischen Lösungsmitteln erlangt (beispielsweise im Vergleich zur konventionellen thermischen Gasphasenabscheidung). Die direkte Graphensynthese mittels chemischer Gasphasenabscheidung auf Si-Substraten mit einer Oxidschicht (Si/SiOx ) ist extrem anspruchsvoll in Bezug auf die großflächige und einheitliche Abscheidung (Lagenanzahl) von Graphen-Monolagen. Das direkte Wachstum von Graphen auf Si/SiOx -Substrat ist interessant, da es frei von unerwünschten Übertragungsverfahren ist und kein Metall-substrat erfordert, welche die erzeugten Graphenschichten brechen lassen können. Um ein homogenes Graphenwachstum zu erzielen wurde durch den Kontakt zweier Si-Wafer, mit ihren Oxidflachen zueinander zeigend, eine lokale Umgebung im chemischen Gleichgewicht erzeugt. Diese Konfiguration der Si-Wafer ist nötig, um eine einheitliche Graphen-Monolage bilden zu können. Eine gründliche Untersuchung des abgeschiedenen Materials zeigt, dass trotz der anfänglichen Keimbildung von runden Inseln facettierte Körner erzeugt werden. Aufgrund der Bestrebung der Graphenkörner ihre (Oberflächen-) Energie zu minimieren, wird eine Facettierung der Körner in polygonaler Form erzeugt, was darin begründet liegt, dass das System idealerweise eine Anordnung von hexagonal geformten Körnern erzeugen würde (niedrigster Energiezustand). Der Prozess ist vergleichbar mit der sechseckigen Zellstruktur einer Bienenstockwabe, welche ein Minimum an Wachs erfordert. Dieser Prozess führt auch zu einer nahezu minimalen Gesamtkorn-grenzlänge pro Flächeneinheit. Diese Tatsache zusammen mit der hohen Qualität der resultierenden Graphenschicht spiegelt sich auch in dessen elektrischer Leistungsfähigkeit wider, die in hohem Maße mit der auf anderen Substraten gebildeten Graphenschichten (inklusive Cu-Substrate) vergleichbar ist. Darüber hinaus ist das Graphenwachstum selbstabschliessend, wodurch ein großes Parameterfenster für eine einfache und kontrollierte Synthese eröffnet wird. Dieser Ansatz zur chemischen Gasphasenabscheidung von Graphen auf Si- Substraten ist leicht skalierbar und gegenüber der Abscheidung auf Metallsubstraten konkurrenzfähig, da keine Substratübertragung notig ist. Darüber hinaus ist dieser Prozess auch für die direkte Synthese anderer zweidimensionalen Materialien und deren Van-der-Waals-Heterostrukturen anwendbar.

Les mousses de carbone vitreux à très forte porosité, qui résultent de la pyrolyse de mousses polymères, ont des propriétés mécaniques et thermiques inadaptées pour certaines applications structurales (absorption de choc, piles à combustible...). Lors de cette étude, des revêtements de pyrocarbone (PyC, à partir de propane) et de carbure de silicium (SiC, issu du mélange CH3SiCl3/H2) ont été mis en oeuvre par dépôt chimique en phase vapeur (CVD) et les conditions expérimentales ont été optimisées afin d’améliorer les propriétés des mousses. Les caractéristiques mécaniques, thermiques et de transport gazeux ont été évaluées respectivement grâce à des tests de compression uniaxiale et des mesures sur bancs de diffusivité flash et de perméabilité. Les propriétés physiques varient dans une grande proportion avec la densité relative. Grâce au contrôle de la composition, de la structure, de l’homogénéité d’épaisseur des dépôts et de la densité relative des mousses, le procédé de CVD permet d’adapter précisément leurs propriétés à une application précise. / High porosity open cell carbon foams, resulting from the pyrolysis polymeric foams, have inadequate properties for structural applications such as shock absorbers or fuel cells. In this study, pyrocarbon (PyC derived from propane) and silicon carbide (SiC from CH3SiCl3/H2 mixtures) coatings were prepared by Chemical Vapour Deposition (CVD) and the experimental conditions were optimized to improve the properties of the foams. The mechanical, thermal and gas transport properties were respectively assessed by uniaxial crushing tests, flash diffusivity and gas permeability measurements. The physical properties vary significantly with the relative density. The CVD process allows the tailoring of the foam properties, for a specific application, through an accurate control of the structure, the composition, the thickness uniformity of the coatings and the relative density of the foams.