Les propriétés structurales et de luminescence de couches minces de TiO2 et Y2O3 dopées terres rares (thulium, terbium et ytterbium) ont été étudiées en vue de les intégrer dans une cellule photovoltaïque comme couche de conversion spectrale du proche UV vers l'infrarouge afin d'en améliorer l'efficacité. Ces couches minces ont été synthétisées par dépôt chimique en phase vapeur à pression atmosphérique à l'aide de précurseurs organo-métalliques et assisté par aérosol (aerosol assisted MOCVD). Les couches minces sont partiellement cristallisées dès la synthèse (400°C pour le TiO2 en phase anatase, 540°C pour Y2O3 en phase cubique). Après traitement thermique la cristallisation est largement améliorée et la luminescence des ions dopant terres rares est obtenue dans les deux matrices oxydes. Le thulium émet dans une large bande située vers 800 nm et l'ytterbium vers 980 nm. Le terbium quand à lui émet dans une gamme située principalement dans le visible. Les spectres d'excitation ont montré que l'absorption des photons se fait via la matrice. En matrice TiO2 une efficacité de transfert d'énergie du Tm3+ vers l'Yb3+ de l'ordre de 20 % a été déterminée pour des teneurs de 0,8 % des deux dopants, ce qui correspond à la limite d'auto-extinction. Le rendement global mesuré est faible, nous avons montré que les causes probables de cette faible valeur sont le manque d'absorption des couches minces pour obtenir l'excitation de l'ion sensibilisateur ainsi que des processus de luminescence et de down conversion pas assez efficaces.

Le graphène épitaxié sur des substrats métalliques est un modèle prometteur pour le développement de nouveaux systèmes hybrides, dans lesquelles les effets d'interface peuvent être exploités pour concevoir de nouvelles propriétés. L'insertion d'espèces entre le graphène et son substrat, une opération connues sous le nom d'-"intercalation", est une approche très puissante à cet égard. Avec l'aide des outils de la physique des surfaces, nous avons étudié trois systèmes graphène/métal, dont deux sont des systèmes hybrides intercalés, et l'autre est un candidat pour un tel système : (i) le graphène/Ir(111) intercalé avec un oxyde ultra-mince, (ii) graphène/Ir(111) intercalé avec des couches sub-atomiques du cobalt et (iii) de graphène sur Re(0001). Nous avons montré que certains défauts, en particulier les ridules (délamination du graphène de son substrat) et d'autres régions courbées du graphène, jouent un rôle crucial, non anticipé, dans le processus d'intercalation. Nous avons également observé que l'intercalation se déroule d'une manière nettement différente sous ultravide et à pression atmosphérique. Dans le premier système, des espèces contenant de l'oxygène entrent à l'extrémité ouverte des ridules et diffusent au long de ces ridules pour former des nano-rubans d'oxyde. Ces rubans modifient le dopage électronique du graphène, ce qui se traduit également par des changements substantiels dans la réponse optique inélastique (Raman) du graphène. Dans le second système, l'efficacité de l'intercalation est apparue dépendante de l'interaction graphène-métal, laquelle varie entre les domaines de graphène orientés différemment sur_(111). Dans ce système, les sites d'entrée pour les espèces intercalées, des régions courbées dans le graphène, ont pu être identifiés grâce à l'observation in_operando (en cours de croissance) du processus. Enfin, la croissance de graphène dans un troisième système (graphène/Re(0001)), a été étudiée afin de permettre le développement de futurs systèmes graphène/Re hybrides supraconducteurs. Dans ce système, nous avons proposé deux voies de croissance, l'une étant basé sur un processus de croissance en surface d'un monocristal massif de Re(0001), l'autre reposant sur la ségrégation en surface, activée thermiquement, du carbone dissout à haute température dans des films minces de Re sur saphir.

Individuals with high levels of plasma triglycerides are at high risk to develop cardiovascular disease (CVD), currently one of the major causes of death worldwide. Recent epidemiological studies show that loss-of-function mutations in the APOC3 gene lower plasma triglyceride levels and reduce the incidence of coronary artery disease. The APOC3 gene encodes for apolipoprotein (APO) C3, known as an inhibitor of lipoprotein lipase (LPL) activity. Similarly, a common gain-of-function mutation in the LPL gene is associated with reduced risk for CVD. LPL is central for the metabolism of lipids in blood. The enzyme acts at the endothelial surface of the capillary bed where it hydrolyzes triglycerides in circulating triglyceride-rich lipoproteins (TRLs) and thereby allows uptake of fatty acids in adjacent tissues. LPL activity has to be rapidly modulated to adapt to the metabolic demands of different tissues. The current view is that LPL is constitutively expressed and that the rapid modulation of the enzymatic activity occurs by some different controller proteins. Angiopoietin-like protein 4 (ANGPTL4) is one of the main candidates for control of LPL activity. ANGPTL4 causes irreversible inactivation through dissociation of the active LPL dimer to inactive monomers. Other proteins that have effects on LPL activity are the APOCs which are surface components of the substrate TRLs. APOC2 is a well-known LPL co-factor, whereas APOC1 and APOC3 independently inhibit LPL activity. Given the important role of LPL for triglyceride homeostasis in blood, the aim of this thesis was to find small molecules that could increase LPL activity and serve as lead compounds in future drug discovery efforts. Another aim was to investigate the molecular mechanisms for how APOC1 and APOC3 inhibit LPL activity. Using a small molecule screening library we have identified small molecules that can protect LPL from inactivation by ANGPTL4 during incubations in vitro. Following a structure-activity relationship study we have synthesized lead compounds that more efficiently protect LPL from inactivation by ANGPTL4 in vitro and also have dramatic triglyceride-lowering properties in vivo. In a separate study we show that low concentrations of fatty acids possess the ability to prevent inactivation of LPL by ANGPTL4 under in vitro conditions. With regard to APOC1 and APOC3 we demonstrate that when bound to TRLs, these apolipoproteins prevent binding of LPL to the lipid/water interface. This results in decreased lipolysis and in an increased susceptibility of LPL to inactivation by ANGPTL4. We demonstrate that hydrophobic amino acid residues that are centrally located in the APOC3 molecule are critical for attachment of this protein to lipid emulsion particles and consequently for inhibition of LPL activity. In summary, this work has identified a lead compound that protects LPL from inactivation by ANGPTL4 in vitro and lowers triglycerides in vivo. In addition, we propose a molecular mechanism for inhibition of LPL activity by APOC1 and APOC3.

Background: In the past 37 years, increased efforts have been directed toward a better understanding of the importance of Hcy in disease and it has now become clear that hyperhomocysteinemia is a major independent risk factor for CVD. Extensive research on the influence of vitamin supplementation leading to reductions in Hcy levels and improvements in cardiovascular function has been done. The importance of exercise in the lowering of cardiovascular risk factors, as well as its favourable influence on cardiovascular function has also been indicated in several studies, however, the limited number of studies investigating the effect of exercise on Hcy concentrations revealed contradicting results. Furthermore, a relationship between Hcy concentration and cardiovascular function with the intervention of an exercise training and a vitamin supplementation programme respectively has also not been investigated. Objective: The objective of this study was to examine the effect of a 12-week exercise training and a 12-week vitamin supplementation intervention respectively on tHcy concentrations and cardiovascular function, and whether the change in tHcy concentration within the different interventions correlated with the change in cardiovascular function. Methods: In a randomised controlled cross-over intervention study, 52 men matched for age, cardiorespiratory fitness levels and cardiovascular risk factors were randomly assigned to one of 3 groups (Group A = exercise training programme, 20-30min. at 70-80% of HRmax; Group B = 400 g folic acid and 25 g vitamin B12 supplement; Group C = control). Group A and B were crossed over for phase 11, and Group C remained the control. The questionnaires were completed, and the body composition variables (BMI, WHR and body fat percentage), cardiovascular function (Finometer), tHcy concentrations and VO2max, were measured before and after each 12-week intervention period. A 6-week washout period separated the crossovers. Results: The ANCOVA, adjusted for age and BMI, showed that the percentage change from baseline to end, corrected for baseline of the tHcy concentration increased significantly (p ≤ .05) by 9.7% with the exercise training intervention and decreased significantly (p ≤ .05) by 12.9%, with the vitamin supplementation intervention. The ANCOVA of the percentage change from baseline to end in cardiovascular function showed that the vitamin supplementation intervention resulted in improvements in cardiovascular function (decreased resting MAP, TPR and increased resting SV, CO, Cw) in comparison to the impairment in cardiovascular function with the exercise training intervention (increased resting DBP, MAP and TPR). The relationship between the tHcy concentration and cardiovascular function at baseline and within each of the different interventions were assessed by partial correlations adjusted for age, BMI and VO2max. Significant (p ≤ .05) relationships only occurred within the vitamin supplementation intervention, where decreased percentage change in tHcy concentration significantly correlated with increased percentage change of resting SV and CO and decreased percentage change of resting TPR. Conclusion: The general conclusion that can be drawn is that a 12-week vitamin supplementation intervention showed increased health related results, e.g. a significant reduction in tHcy concentration, an improvement in cardiovascular function and a significant positive relationship between these b o factors, in comparison to the 12-week exercise training intervention that significantly increased the tHcy concentration and did not show increased health related results. Due to inadequate compliance to the exercise training intervention, no conclusion can be drawn with regard to the effect of exercise training on tHcy concentrations and cardiovascular function. / Thesis (M.Sc. (Human Movement Science))--North-West University, Potchefstroom Campus, 2007

Ce travail de thèse porte sur l'étude de nouveaux phénomènes vibratoires dans les systèmes Nano-électromécaniques (NEMS) conçus à partir de nanofils (NFs) SiC ou de nanotubes de carbone (NCs) résonants. La configuration encastré-libre permet d'effectuer l'émission de champ (EC) pour caractériser nos échantillons et notamment mesurer le module de Young et le facteur de qualité (Q) de nos NEMS. Le chauffage du résonateur permet d'accroître fortement la valeur de Q des nanofils SiC (Qmax = 159 000). Les auto-oscillations observées sous EC sont obtenues seulement par l'application d'une tension continue et permettent un taux de conversion AC/DC de l'ordre de 50%. L'utilisation de NFs très résistifs couplée au courant d'EC est indispensable pour engendrer ces oscillations spontanées. La réalisation d'une nanoradio sous EC permet la démodulation d'un signal AM ou FM grâce à la résonance d'un NC. Nous décrivons une méthode originale pour exciter les vibrations d'un NF à partir du faisceau d'électrons d'un microscope électronique. L'évolution de la charge au bout du NF est la principale cause de ces auto-oscillations. La configuration encastré-encastré consiste à obtenir un transistor à base de NCs suspendus. Les composants sont caractérisés électriquement et mécaniquement dans un testeur sous pointe sous ultra vide à partir de techniques dites de mixing. La fréquence de résonance de ces échantillons est de l'ordre de 100 MHz et la démodulation d'un signal FM est réalisée pour la première fois dans cette configuration de NEMS. Pour l'ensemble des phénomènes découverts et traités dans ce manuscrit, un modèle et les simulations qui en découlent sont présentés et commentés

Compared to wafer based solar cells, thin film solar cells greatly reduce material cost and thermal budget due to low temperature process. Monolithically manufacturing allows large area fabrication and continuous processing. In this work, several photovoltaic thin films have been developed by rf-PECVD including a-Si:H and μc-Si, both intrinsic and doped on Corning 4 inch glass substrate at low temperature. The conductivity of n type and p type μc-Si at 180ºC was 17S/cm and 7.1E-2S/cm, respectively. B dopants either in a-Si:H or μc-Si films require higher plasma power to get active doping. The B2H6-to-SiH4 flow ratio for p type μc-Si lies from 0.01 to 0.025. Chamber conditions have critical effect on film quality. Repeatable and superior results require a well-established cleaning passivation procedure. Moreover, μc-Si films have been deposited from pure silane on glass substrate by modified rf-ICP-CVD. The deposition rate has been dramatically increased to 5Å/s due to little H2 dilution with crystalline fraction was around 69%, and 6.2Å/s with crystalline fraction 45%. Microstructure started to form at 150ºC with a thin incubation layer on the glass substrate, and became fully dense conical conglomerates around 300nm where conductivity and crystallinity saturated. Additionally, a-SiGe:H films have been developed by modified rf-ICP-CVD. The optical band gaps have been varied from 1.25 to 1.63eV by changing SiH4-to-GeH4 ratio. Also high temperature resulted in low bandgap. Cross-section TEM showed some microcrystllites appeared near interface region. Heterojunction solar cells on p type c-Si wafer have been fabricated using films developed in this thesis. Interference fringes in EQE disappeared on either textured substrate or cells with lift-off contacts. Maximum EQE was 87% around 700nm. I-V curves have also been studied where the interesting kink suggests a counter-diode has formed between emitter region and contacts.

This report details work toward the fabrication of a single-electron transistor created from a single-walled carbon nanotube (SWNT). Specifically discussed is a method for growing carbon nanotubes (CNTs) via carbon vapor deposition (CVD). The growth is catalyzed by a solution of 0.02g Fe(NO3)3·9H2O, 0.005g MoO2(acac)2, and 0.015g of alumina particles in 15mL methanol. SWNT diameter ranges from 0.6 to 3.0 nm. Also discussed is a method to control nanotube growth location by patterning samples with small islands of catalyst. A novel “maskless” photolithographic process is used to focus light from a lightweight commercial digital projector through a microscope. Catalyst islands created by this method are approximately 400 μm2 in area.

Cutting tools are subject to extreme environment during processing, with hightemperatures and pressures. CVD coatings are used to increase lifetime andperformance of the WC/Co composite. Residual stresses in the coatings areinteresting as they may be destructive or constructive for the material duringoperation. Blasting is used to change the as-deposited tensile stress to compressive.The usefulness of X-ray diffraction (XRD) and nanobeam diffraction (NBD) forcharacterization of strains in the different coating layers has been investigated. XRDwith different anode materials has been used to determine the macrostress in thelayers and an attempt was done to calculate the average microstrain and crystallitesize. NBD was used to study the microstrain within single grains of the differentmaterials. A specimen preparation method has been developed for the studiedsamples using the FIB.The XRD analysis shows that the measurement condition is of great importanceduring stress measurements. The macrostress of the different samples show that theZrCN type coating is less stressed than the TiCN type coating after deposition. It isalso shown that the ZrCN type coating is less affected by the blasting. Determinationof microstrain and crystallite size from XRD needs further development.The NBD is a good method to evaluate microstrain within single grains, or betweengrains oriented in the same zone axis. The analyses show more strain within thegrains after blasting. The measurements indicate more strain variation in the Al2O3layer in the TiCN system compared to the ZrCN system.

L’étude présentée est consacrée à l’usinabilité de la fonte à graphite vermiculaire. Celle-ci se situe entre la fonte à graphite lamellaire et la fonte à graphite sphéroïdale par rapport à la forme du graphite constituant ce matériau. Elle est utilisée depuis plus de cinq ans dans les blocs moteurs diesel afin d’améliorer les performances et de diminuer les rejets atmosphériques pour respecter les nouvelles normes Européennes. Pour évaluer l’usinabilité d’un matériau, il faut s’étalonner par rapport à un matériau de référence. Dans notre cas, la fonte à graphite vermiculaire a été comparée à la fonte à graphite lamellaire. Des essais de tractions ont permis d’obtenir les propriétés mécaniques du lot de matière utilisé pour la campagne d’essais d’usinage ; ceci, afin de se situer dans la gamme de ce type de fonte. Les plaquettes d’usinage ont été caractérisées par nano-indentation. Les revêtements PVD et CVD ont subit des essais de micro-rayure afin de caractériser leur adhésion sur leurs substrats respectifs. La mise en place d’un plan d’expérience a permis de limiter le nombre de plaquettes d’usinage prototypes à réaliser. Des essais tribologiques de type pion/disque ont révélé des pistes exploitables pour la compréhension des phénomènes de frottement et d’usures mis en jeu lors de l’usinage de la fonte à graphite vermiculaire. / This study deals with machinability of compacted graphite iron. This material is in-between grey cast iron and nodular cast iron due to the graphite particle shape. It is used for manufacturing diesel engine blocks so as to increase performances and reduce carbon emissions to comply with Euro 5 norm. It is necessary to compare one material to a reference material to evalute machinability criterium. In our case, compacted graphite iron has been compared to grey cast iron. Tensile tests have given us mechanical properties of our test pieces batch used for machining tests. It helped us to qualify the material in its own material range. Inserts have been characterized by nanoindentation. PVD and CVD coatings were benchmarked in microscratch way to determine their respective adhesion to theirs substrates A design of experiment has been setted up so as to reduce number of inserts protypes to be manufactured. Pin on disk tribologic tests gave few hints to have a better understanding of friction phenomena and wear during compacted graphite iron machining.

Submitted by MARIA CLAUDIA COSTA DE OLIVEIRA BOTAN null (maclau_oliveira@hotmail.com) on 2017-09-01T16:19:06Z No. of bitstreams: 1 tese_final_Maria_Claudia_Botan.pdf: 4509077 bytes, checksum: 9a0c384b0ba382775d7f33ea6d5ec76e (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-09-01T16:48:26Z (GMT) No. of bitstreams: 1 botan_mcco_dr_guara.pdf: 4509077 bytes, checksum: 9a0c384b0ba382775d7f33ea6d5ec76e (MD5) / Made available in DSpace on 2017-09-01T16:48:26Z (GMT). No. of bitstreams: 1 botan_mcco_dr_guara.pdf: 4509077 bytes, checksum: 9a0c384b0ba382775d7f33ea6d5ec76e (MD5) Previous issue date: 2017-08-04 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A escassez de água potável vem impulsionando diversas pesquisas ao redor do mundo, por este ser um elemento vital e por sua obtenção envolver um grande paradigma, afinal não há efetivamente produção de água, o que existe é uma mudança de estado físico por meio do ciclo hidrológico. É preciso trazer segurança ao abastecimento sem abrir mão do caráter sustentável, utilizando materiais de baixo impacto ambiental associando-os a fontes renováveis de energia para seu funcionamento. Neste sentido, o presente estudo consiste na busca de melhorias de um condensador de vapor atmosférico, utilizando para tal, filmes finos de diamante como trocador de calor. Como este material apresenta condutividade térmica maior que a do cobre e do alumínio, visa-se agregar eficiência energética ao sistema. Dentre os procedimentos tomados identificou-se que o substrato de Silício do tipo P-Boro (111) foi o mais adequado para o crescimento dos filmes, obteve-se diferentes espessuras para comparação de desempenho no condensador e verificou-se a viabilidade técnica da proposta, pois foi possível realizar condensação utilizando o filme de diamante. De maneira geral, não há produção de condensado em umidades relativas inferiores a 50%. A partir de umidades superiores a 80 %, a amostra mais eficiente, no quesito produção de condensado, é a amostra de 4 h de deposição, que atinge o índice de 6 L.h-1.m². O custo ainda se mostra maior se comparado ao cobre e ao alumínio, de qualquer maneira o processo de condensação do vapor apresenta-se como uma alternativa de fonte de abastecimento em locais onde este bem encontra-se de forma escassa, como por exemplo, em plataformas de petróleo e na região árida do Nordeste brasileiro. / The shortage of drinking water has been driving several researches around the world, because its obtaining involves a great paradigm, after all there is no effective production of water, but there is a change of physical state through the hydrological cycle. It is necessary to bring security to the supply without abandoning the sustainable character, using materials of low environmental impact associating them with renewable sources of energy for its operation. In this sense, the present study consists in the search for improvements of an atmospheric vapor condenser, using thin films of diamond as heat exchanger. As this material has higher thermal conductivity than copper and aluminum, it is aimed to add energy efficiency to the system. Among the procedures taken it was found that P-Boron type silicon substrate (111) was the most suitable for the growth of the films, different thicknesses were obtained for the comparison of performance in the condenser and the technical feasibility of the proposal was verified, because it was possible to perform condensation using the diamond film. In general, there is no condensate production at relative humidity of less than 50%. From the humidities more than 80%, the most efficient sample, in the case of condensate production, is the sample of 4 h deposition, which reaches the index of 6 L.h-1 .m². The cost is still unfeasible compared to copper and aluminum, however, the vapor condensation process is an alternative source of supply in places where it is scarce, such as in oil platforms in the arid region of the Brazilian Northeast.