Cette thèse présente la synthèse de graphène par CVD catalytique sur feuille de cuivre, wafers de silicium revêtus de nickel et sur mousse de nickel. Les dépôts ont été réalisé à partir de méthane et d'éthylène. Pour l'ensemble de ces substrats, les études faites ont permis de mieux appréhender les mécanismes de croissance et de déterminer les paramètres opératoires optimaux. Des tests applicatifs ont été effectué pour utiliser le graphène synthétisé comme électrode d'OLED et de batterie Li-ion. / This study concerns graphene synthesis by catalytic CVD (Chemical Vapor Deposition) on copper foils, silicon wafers coated with nickel and nickel foam. Deposits have been synthesized from methane and ethylene. For the whole substrates studied, the results obtained have allowed to better understand the mechanisms of nucleation/growth of graphene and to determine the optimal operating parameters. Some applicative tests have been performed in the fields of OLED and Li-ion battery.

No description available.

Carbon Nanotubes (CNTs) have great potentials for Field Electron Emission (FEE) and Flow Boiling Heat Transfer (FBHT) applications. However, their weak adhesion on metallic substrates limits the development of CNTs in both applications. Diamond has high thermal conductivity and develops strong bonding with CNTs. The development of a diamond interlayer between CNTs and substrates is a feasible approach to address the adhesion problems. The purpose of this research was to develop a new CNT-based materials with a diamond interlayer for FEE and FBHT applications by focusing on four objectives: (1) enhancement of diamond thin film adhesion on a Cu substrate, (2) improvement of the CNT FEE stability, (3) reduction of the CNT FEE turn-on field, and (4) investigation of the FBHT performance of CNT based structures. The CNTs and diamond thin films in this thesis were prepared by Microwave Plasma enhanced Chemical Vapor Deposition (MPCVD) and Hot Filament enhanced Chemical Vapor Deposition (HFCVD). The structure and chemical states of the diamond films and CNTs were characterized by Scanning Electron Microscopy (SEM), cross-sectional Transmission Electron Microscopy (TEM), X-Ray Diffraction (XRD), Raman spectroscopy, synchrotron based X-ray Absorption Spectroscopy (XAS). To deposit diamond thin films on a Cu substrate with sufficient adhesion strength, a sandblasting pretreatment and alloying with a tiny amount of Al were investigated. The adhesion of diamond thin films to substrates was evaluated by Vickers micro-hardness indentation. The FEE stability and turn-on field were measured by a Keithley 237 high voltage measuring unit. The FBHT property of the structures was tested repeatedly at different flow velocities to explore the dependence of heat transfer performance on certain parameters, including the flow patterns, Critical Heat Flux (CHF), and stability. The results show that sandblasting pretreatment increases the surface roughness and surface defect density, thereby increasing diamond nucleation density and adhesion to the Cu substrate. Al alloying appears to inhibit the formation of graphite at the interface between diamond and the Cu substrate, which improves the chemical bonding between diamond and the Cu substrate and increases the adhesion strength between them. The FEE testing results show that ultra-high FEE stability (more than 5000 minutes) was achieved for the CNTs with a diamond interlayer. This is attributed to the good contact at the diamond-CNT and diamond-substrate interfaces. The main factors that affect the CNT FEE turn-on field were also studied. By optimizing the structure, an FEE turn-on field of 5.1 V/μm was achieved and an emission barrier model for CNTs with a diamond interlayer on Cu substrate was used to explain the results. FBHT testing was done on CNTs with different structures and the results show that high heat transfer efficiency can be achieved on CNTs with a diamond interlayer at low mass fluxes.

No description available.

Steel turning inserts cemented carbides have a binder phase consisting of cobalt (Co). However, in recent years a study from the United States National Toxicity Program (NTP) found that cobalt powder is carcinogenic upon inhalation. The European Union's REACH have therefore also classified cobalt powder as carcinogenic upon inhalation. The worldwide search to find a replacement has therefore lately intensified. It is important that the alternative binder phase has no negative effects on the properties of the insert. In this thesis the adhesion between a multilayer ceramic chemical vapor deposition (CVD) coating and a cemented carbide with the alternative binder phases consisting of iron (Fe), nickel (Ni) and cobalt (Co) has been studied. First of all, the fracture surfaces showed that the CVD coating was able to grow on all cemented carbides, regardless of which binder phase. To evaluate the adhesion, scratch tests were performed on all samples. The results from the scratch tests were not as expected. No chipping of the coating down to the cemented carbide occurred on any of the samples and the samples with the hardest cemented carbide did not get the highest critical load, which it should according to the literature if all other parameters were the same. Instead the sample with the binder phase consisting of 73 wt% iron and 27 wt% nickel had the highest critical load. This is thought to be due to that during the scratch test the binder phase in this cemented carbide would most likely transform into deformation martensite.

For two decades, single-wall carbon nanotubes (SWCNTs) have captured the attention of the research community, and become one of the flagships of nanotechnology. Due to their remarkable electronic and optical properties, SWCNTs are prime candidates for the creation of novel and revolutionary electronic, medical, and energy technologies. However, a major stumbling block in the exploitation of nanotube-based technologies is the lack of control of nanotube structure (chirality) during synthesis, which is intimately related to the metallic or semiconductor character of the nanotube. Incomplete understanding of the nanotube growth mechanism hinders a rationale and cost-efficient search of experimental conditions that give way to structural (chiral) control. Thus, computational techniques such as density functional theory (DFT), and reactive molecular dynamics (RMD) are valuable tools that provide the necessary theoretical framework to guide the design of experiments. The nanotube chirality is determined by the helicity of the nanotube and its diameter. DFT calculations show that once a small nanotube 'seed' is nucleated, growth proceeds faster if the seed corresponds to a high chiral angle nanotube. Thus, a strategy to gain control of the nanotube structure during chemical vapor deposition synthesis must focus on controlling the structure of the nucleated nanotube seeds. DFT and RMD simulations demonstrate the viability of using the structures of catalyst particles over which nanotube growth proceeds as templates guiding nanotube growth toward desired chiralities. This effect occurs through epitaxial effects between the nanocatalyst and the nanotube growing on it. The effectiveness of such effects has a non-monotonic relationship with the size of the nanocatalyst, and its interaction with the support, and requires fine-tuning reaction conditions for its exploitation. RMD simulations also demonstrate that carbon bulk-diffusion and nanoparticle supersaturation are not needed to promote nanotube growth, hence reaction conditions that increase nanoparticle stability, but reduce carbon solubility, may be explored to achieve nanotube templated growth of desired chiralities. The effect of carbon dissolution was further demonstrated through analyses of calculated diffusion coefficients. The metallic nanocatalyst was determined to be in viscous solid state throughout growth, but with a less solid character during the induction/nucleation stage.

Chronic noncommunicable diseases (NCDs) are the largest contributor to mortality rates worldwide including in low- and middle- income countries (LMICs) which already suffer from high rates of infectious disease. Among the four major NCDs that cause 38 million deaths annually, cardiovascular disease (CVD) causes 17.5 million of these annual deaths. The primary risk factor of CVD is hypertension. Kenya, a developing country in Sub-Saharan Africa, has a high rate of hypertension with low (2.6%) management rates. Prior research from our lab has identified a population of Kenyans with a high prevalence of hypertension that is not statistically correlated with typical known risk factors such as obesity, hypercholesterolemia, and behaviors of smoking and lack of exercise. This study investigated the hypothesis that high dietary salt consumption and low K+ dietary intake are contributing to the etiology of high blood pressure in this community. To test our hypothesis, two spot urine samples representing nocturnal excretions (evening and morning) and blood pressure measurements were collected from 135 participants. All samples were analyzed for Na+, K+ and Cl- content using the Smartlyte Electrolyte Analyzer. The average of each spot urine sample was extrapolated to an estimated 24-h value by the method of Mills, et al. The overall population mean urine electrolyte excretion values for Na+, K+ and Cl- were 170.6 ± 89.3 mmol/L, 82.0 ± 54.0 mmol/L, and 87.7 ± 42.1 mmol/L, respectively. While these values fall within the suggested levels for Na+ (40-220 mmol/L) and K+ (25-125 mmol/L), they are under normal excretion levels for Cl- (110-250mmol/L). Overall ion excretion was higher in females than males, although only K+ values were statistically significant (p < 0.05). Analysis of Na+ and Cl- excretion from individuals stratified by blood pressure, revealed significant differences (p < 0.05) between normotensive and hypertensive stage I individuals for both electrolytes (57.9 mmol/L vs. 88.9 mmol/L and 65.5 mmol/L vs. 96.7 mmol/L, respectively). Overall, these results suggest that our sample population consumes dietary salt within a normal range and thus, the observed prevalence of hypertension likely results from other genetic and environmental factors.

O Grafeno tem sido estudado há 60 anos, mas só foi desde sua primeira obtenção mediante esfoliação de grafite em 2004 por Novoselov, que obteve grande interesse por parte de pesquisadores, pois tem uma série de notáveis propriedades físicas e químicas que dificilmente são encontradas num mesmo material, o que o torna uma ferramenta de primeira ordem em muitas aplicações de diversos campos. Além disso, sua produção se limita a pequenas folhas, com defeitos e empilhadas formando multicamadas, o qual não permite seu uso em nível industrial. Isso demanda não só que o grafeno seja produzido em grande escala, mas também conservando suas propriedades. O presente trabalho reporta o estudo e estabelecimento de condições para o crescimento de folhas de grafeno, utilizando técnicas de deposição química na fase de vapor a pressão ambiente (APCVD) catalítica, e deposição química na fase vapor assistida por plasma (PECVD), também catalítica, com filmes finos de Níquel e Cobre como metais catalisadores, visto que são as técnicas e metais que tem reportado melhores resultados. Desta forma, esta pesquisa foi encaminhada a um ajuste das variáveis que intervém nas duas técnicas, tais como os gases, seus fluxos e relação entre eles, a temperatura, o tempo de deposição e as espessuras do catalisador. No caso do PECVD, a potência de RF para a geração do plasma e a pressão. Os filmes foram caracterizados por microscopia Raman, que permite ter uma avaliação aproximada do número de camadas e os defeitos presentes no material, e por microscopia eletrônica de varredura (MEV), que permite observar a morfologia das amostras e a possível presença de grafeno, e assim ter certeza da qualidade do grafeno enquanto a continuidade e tamanho das folhas. Além disso, mediante Espectroscopia de raios X por dispersão de energia (EDS), instrumento associado ao MEV, é possível identificar os elementos presentes na amostra em pontos específicos e sua porcentagem. Estes análises revelaram que o grafeno obtido foi de grande área (1 cm2) com alta cristalinidade e poucos defeitos pontuais. / Graphene has been studied for 60 years, but was only since its first achievement by graphite exfoliation in 2004 by Novoselov that got great interest by researches, because it has remarkable physical and chemical properties which are hardly found in a single material, which makes it a first-order tool for many applications in several fields. Besides that, its production is limited to small sheets with defects and stacked in multilayers, which does not allow its use at industrial level, that requires not only a large scale production of graphene but also conservation of its properties. This work reports the study and find suitable conditions for the growth of graphene sheets, using catalytic atmospheric pressure chemical vapor deposition (APCVD) and plasma enhanced chemical vapor deposition (PECVD) techniques and thin nickel and copper films as catalysts. This choice is based on the fact that both, these techniques and the metals had lead to better reported results. Thus, this research is focused on the adjustment of the parameters that intervene in the two techniques, such as precursor gases, their flows and the relationship among them, temperature, deposition time and the catalyst thickness. In the case of the PECVD, the RF power to generate the plasma and the deposition pressure. The films were characterized by Raman spectroscopy, which allows an approximate evaluation of the number of layers and the defects in the material, and by Scanning Electron Microscopy (SEM), which allows to observe the morphology of the deposited layers, and thus to ensure the quality of the graphene as far as the continuity and size of the sheets are concerned. In addition, energy dispersive X-ray spectroscopy (EDS) associated to the SEM instrument was utilized to identify the elements present in particular locations of the sample as well as their percentage. These group of analyses revealed that the obtained graphene achieved areas about 1 cm2 with high crystallinity and low punctual defects.

No description available.

GaN is a monocrystalline material that can be grown using metallo-organic chemical vapour deposition (MOCVD), and has desirable mechanical and semiconducting properties for operating as a sensor. It has a Young’s modulus of 250 to 350 GPa, which shows little decrease with respect to temperature beyond 400°C. GaN also exhibits piezoelectric and piezoresistive effects, meaning that it will generate a charge and its electrical resistance will change when the material is strained respectively. In this PhD, GaN has been used as the base material for pressure sensors that potentially can be used in excess of 400°C and at a pressure in excess of 50 bar (5 MPa), with potential applications in aerospace and oil exploration. The pressure sensor is a circular diaphragm created from a GaN/sapphire wafer, and was designed and tested in order to determine if GaN can act as a sensing material in these environments. In addition to the diaphragm sensor, GaN templates that can potentially be used for sensors were grown using an epitaxial layer overgrowth (ELOG) method. These sensors are potentially more mechanically robust than similar templates etched out of GaN/sapphire wafers because they will have less inbuilt strain due to lower dislocation densities. It was possible to release beams and cantilevers from GaN ELOG templates. Mechanical probe tests were undertaken on these devices to see if they were fully released and robust. GaN single crystal growth requires a substrate material, such as (111) silicon or (0001) sapphire, meaning that the thermal properties of the substrate are important for a device operating in excess of 400°C. GaN high electron mobility transistors are heat sensitive, experiencing a decrease in current between the drain and source terminals as the temperature increases. Therefore a GaN-based sensor needs a substrate with the highest possible thermal conductivity to act as a heat sink, which means removing as much heat as possible from the GaN sensor. Diamond has superior thermal conductivity to both sapphire and silicon, so a novel silicon/polycrystalline diamond composite substrate has been developed as a potential GaN substrate. Polycrystalline diamond (PD) can be grown on 4 inch diameter wafers using hot filament chemical vapour deposition (CVD), on (111) silicon (Si) from which single crystal GaN epitaxy can also be grown. In order for the (111) Si/PD composite substrates to be useful heat sinks, the Si layer needs to be less than 2 m. PD was initially grown on 525 to 625 m thick Si wafers that required thinning to 2 m. Achieving this Si layer thickness is difficult due to the presence of tensile stress in the Si caused by a mismatch in the coefficients of thermal expansion (CTEs) between Si and PD. This stress causes the wafer to bow significantly and has been modelled using ANSYS FE software. The models show that the bow of the wafer increases when it is thinned, which will eventually cause the Si layer to delaminate at the Si/PD interface due to poor adhesion and a build up for shear stress. When the Si layer is mechanically thinned, the Si layer can crack due to clamping. The experimental wafer bow and micro-Raman measurements validate the model for when the silicon layer is thicker than 100 m and these results show that an alternative processing route is required.