The uniform dispersion of the nano fillers without agglomeration in a polymeric matrix is widely adapted for the purpose of mechanical properties enhancement. In the context to biomedical applications, the type and amount of nanoparticles can potentially influence the biocompatibility. In order to address these issues, High Density Polyethylene (HDPE) based composites reinforced with graphene oxide (GO) were prepared by melt mixing followed by compression moulding. In an attempt to tailor the dispersion and to improve the interfacial adhesion, polyethylene (PE) was immobilized onto GO sheets by nucleophilic addition-elimination reaction. A good combination of yield strength (ca. 20 MPa), elastic modulus (ca. 600 MPa) and an outstanding elongation at failure (ca. 70 %) were recorded with 3 wt % polyethylene grafted graphene oxide (PE-g-GO) reinforced HDPE composites. Considering the relevance of protein adsorption as a biophysical precursor to cell adhesion, the protein adsorption isotherms of bovine serum albumin (BSA) were determined to realize three times higher equilibrium constant (Keq) for PE-g-GO reinforced HDPE composites as compared to GO reinforced composites. In order to assess the cytocompatibility, osteoblast cells (MC3T3) were grown on HDPE/GO and HDPE/PE-g-GO composites, in vitro. The statistically significant increase in metabolically active cell was observed, irrespective of the substrate composition. Such observation indicated that HDPE with GO or PE-g-GO addition (upto 3 wt %) can be used as cell growth substrate. The extensive proliferation of cells with oriented growth pattern also supported the fact that tailored GO addition can support cellular functionality, in vitro. Taken together, the experimental results suggest that the PE-g-GO in HDPE can effectively be utilized to enhance both mechanical and cytocompatibility properties and can further be explored for potential biomedical applications.

Cette thèse porte sur la synthèse et la caractérisation de nouvelles phases bidimensionnelles par microscopie électronique in-situ, notamment la silice (SiO2), des cages nanométriques de carbone similaire à des molécules C20 et le chalcocite (β-Cu2S). Ces études ont permis de mettre en évidence les conditions préalables de croissance afin que celle-ci soit reproductible. La caractérisation de ces structures a été réalisée par imagerie haute résolution (HRTEM) ainsi que par spectroscopie de perte d’énergie (EELS). La première partie de la thèse est consacrée à l’étude de la nucléation et la croissance in-situ d’une phase cristalline 2D ordonnée et désordonnée sur différents métaux de transition (Co, Ru, Fe) ainsi qu’une phase 1D qui croît le long des marches atomiques sur la surface métallique. La seconde partie est consacrée à la croissance in-situ de cages de carbone d’un diamètre de l’ordre de 0.36 nm en présence d’un catalyseur métallique, tel que Co, Fe et Ru. La dernière partie est consacrée à l’étude de la croissance de la plus fine structure cristalline du β-Cu2S sur la surface du graphène. Toutes ces études ont été appuyées par des simulations d’images de microscopie. / The aim of this thesis is the synthesis and characterization of new two-dimensional phases in an in-situ transmission electron microscopy experiment. These studies concerned the nucleation and growth of three deferent materials: quasi-two-dimensional silica (SiO2), the smallest possible carbon cages with the size of C20, and two-dimensional chalcocite (β-Cu2S). The characterization of these structures has been performed using high resolution imaging (HRTEM) and electron energy-loss spectroscopy (EELS). The first part of this thesis is devoted to the study of the nucleation and growth of an ordered or disordered 2D crystalline phase of silica on different substrates (Co, Ru, Fe) and a 1D silica phase grown at atomic steps of a metal surface. The second part illustrates the in-situ growth of the smallest possible carbon cages with a diameter of about 0.36 nm on catalytically active metal surfaces such as Co, Fe, or Ru. The last part is devoted to the growth of the thinnest stable layer of β-Cu2S on a graphene surface. All these studies were accompanied by image simulations.

Cette thèse présente une étude des impulsions électroniques ultra-brèves en utilisant le nouveau microscope électronique en transmission ultrarapide (UTEM) à Strasbourg. La première partie porte sur le mode d’opération stroboscopique, basé sur l’utilisation d’un train d’impulsions d’électrons de l’ordre de la picoseconde pour l’étude des phénomènes réversibles ultrarapides. L’étude paramétrique effectuée a permis de révéler les dynamiques fondamentales des impulsions électroniques. Des mécanismes inconnus jusqu’alors et décisifs dans les caractéristiques des impulsions ont été dévoilés. Il s’agit des effets de trajectoire, qui limitent la résolution temporelle, et du filtrage chromatique, qui impacte la distribution en énergie et l’intensité du signal. Ces connaissances permettent aujourd’hui un paramétrage affiné de l’UTEM de manière à satisfaire les divers besoins expérimentaux. La deuxième partie concerne l’installation du mode d’opération complémentaire : le mode « singel-shot ». Ce mode fait appel à une impulsion unique d’intensité élevé et d’une durée de l’ordre de la nanoseconde pour l’étude des phénomènes irréversibles. L’UTEM de Strasbourg étant le premier instrument single-shot équipé d’un spectromètre de perte d’énergie des électrons (EELS), l’influence de l’aberration chromatique a pu été étudiée en détail. Elle s’est dévoilée être une limitation majeure pour la résolution en imagerie, nécessitant d’ajuster le bon compromis avec l’aberration sphérique d’une part et l’intensité du signal d’autre part. Enfin, la faisabilité de mener des études en EELS ultrarapide avec une seule impulsion nanoseconde a pu être démontrée, ceci constituant une première mondiale. Ce résultat très prometteur ouvre un tout nouveau domaine d’expériences résolu en temps. / This thesis presents a study of ultrashort electron pulses by using the new ultrafast transmission electron microscope (UTEM) in Strasbourg. The first part focuses on the stroboscopic operation mode which works with trains of picosecond multi-electron pulses in order to study ultrafast, reversible processes. A detailed parametric study was carried out, revealing fundamental principles of electron pulse dynamics. New mechanisms were unveiled which define the pulse characteristics. These are trajectory effects, limiting the temporal resolution, and chromatic filtering, which acts on the energy distribution and signal intensity. Guidelines can be given for optimum operation conditions adapted to different experimental requirements. The second part starts with the setup of the single-shot operation mode, based on intense nanosecond electron pulses for the investigation of irreversible processes. Having the first ns-UTEM equipped with an electron energy loss spectrometer, the influence of chromatic aberration was studied and found to be a major limitation in imaging. It has to be traded off with spherical aberration and signal intensity. For the first time, the feasibility of core-loss EELS with one unique ns-electron pulse is demonstrated. This opens a new field of time-resolved experiments.

Les phénomènes quantiques des nanostructures peuvent être une opportunité pour le développement d’une nouvelle génération de cellules photovoltaïques. Ce travail décrit la synthèse et les caractérisations de nanoparticules de silicium dans une matrice d’oxynitrure de silicium. Il est possible d’obtenir des nanoparticules de silicium de diamètre compris entre 3 et 7 nm dans des matrices allant du nitrure de silicium à l’oxyde de silicium. Les propriétés des nanoparticules dépendent très fortement de la composition de la matrice. Afin d’accroître la conduction dans ces couches diélectriques, nous avons effectué un dopage électrique par implantation ionique. La localisation et la densité des ions implantés ont été observées par des techniques associées de microscopie électronique en transmission et de rayons X. Une augmentation de la conduction a été démontrée lors du dopage permettant d’observer un effet photovoltaïque sur une structure comportant des nanoparticules de silicium. / Quantum effects in nanostructures exhibit properties that can be very useful for the development of a new generation of solar cells. We investigated the synthesis of silicon nanostructures in silicon oxynitride made by a plasma enhanced chemical vapour deposition technique. Thus, silicon nanoparticles of diameter between 3 and 7 nm were obtained in different matrix ranging from silicon oxide to silicon nitride. The properties highly depend on the composition of the matrix. We also study the incorporation of impurities in the films with the aim of increasing the electrical conductivity of the structure. This was done by implanting different ions in the structure followed by thermal annealing. We have investigated the position of the ion and its content in the composite by combining Transmission Electron Microscopy and X-ray diffraction. Finally, N+/P junctions were fabricated using highly doped films containing silicon nanoparticles and a photovoltaic effect was demonstrated.

Conventional casting alloys Al-7Si-Mg A356/7 contain between 6.5 and 7.5% Si, together with 0.25-0.7% Mg and are used for critical castings in the automotive and aerospace industries. These alloys are also the most popular alloys used for semi-solid metal (SSM) forming due to good castability and fluidity imparted by the large volumes of the Al-Si eutectic. Despite their industrial importance, there is a lack of detailed research work revealing precipitate micro- and nanostructural evolution during aging of these alloys compared with the Al-Mg-Si 6000 series wrought alloys. This study characterises the heat treatment response of SSM-processed Al-7Si-Mg alloys in comparison with conventionally liquid cast alloys (investment casting and gravity die casting). It is shown that, provided that the maximum quantity of the alloy’s Mg is placed into solid solution during solution treatment, and that the alloy’s Fe content is within specification, the response to age hardening of Al-7Si-Mg alloys is independent of the processing technique used. The nanostructural evolution of Al- 7Si-Mg alloys after artificial aging with and without natural pre-aging has been characterized using transmission electron microscopy and atom probe tomography and correlated with hardness and mechanical tensile properties. The number densities and Mg:Si ratios of solute clusters, GP zones and β"-needles were determined. The heat treatment response of SSM-processed casting alloys A356/7 alloys are also compared with SSM-processed Al-Mg-Si 6000 series wrought alloys, with the advantage of having similar globular microstructures. The high Si-content of the casting alloys compared to the wrought alloys offers several advantages, including a faster artificial aging response (shorter T6 aging cycles), higher strength for comparable Mg contents and less sensitivity to prior natural aging on peak strength. Finally, an age-hardening model was developed for the Al-7Si-Mg alloys, including a method of incorporating the effects of changes in Mg-content on the aging curves. / Thesis (PhD(Eng))--University of Pretoria, 2011. / Materials Science and Metallurgical Engineering / unrestricted

Le but de cette thèse a été d'étudier les propriétés structurales et optiques de puits quantiques (PQs) d’InGaN/(Al)GaN obtenus par épitaxie en phase vapeur d’organométalliques. Différentes approches ont été mises en œuvre pour atteindre une émission dans le vert-jaune: la première utilisant une concentration d'indium ≥ 20% avec un PQ d’InGaN d’épaisseur <3.0 nm et vice versa. L'effet d'une couche d’encapsulation a également été étudié. Les techniques de microscopie à force atomique, de diffraction des rayons X, de photoluminescence (PL) et surtout de microscopie électronique à transmission (MET) ont été utilisées pour caractériser ces structures. Les épaisseurs des PQs et les compositions en indium ont été déterminées par le traitement numérique des franges de réseau dans les images MET haute résolution en section transverse. Un traitement original a été développé pour analyser quantitativement les fluctuations de l’épaisseur des PQs. L'analyse structurale des PQs ayant une composition en In élevé a montré que les défauts structuraux sont créés dans les PQs. La nature et la densité de ces défauts ont été déterminées et différents mécanismes pour leur formation ont été proposés. Il a également été montré que quelques monocouches d’encapsulation de GaN ou d’AlGaN déposées à la température de croissance des PQs limitent l’évaporation et/ou la diffusion d’indium. Ce procédé permet d’étendre la longueur d'onde d'émission avec une réduction de la dégradation de l'efficacité de la PL. Mon travail propose quelques pistes afin d'obtenir un bon compromis entre les paramètres contradictoires qui régissent l'efficacité des PQs émettant dans le vert-jaune. / The goal of this thesis was to study the structural and optical properties of InGaN/(Al)GaN multiple QWs grown by metal organic chemical vapor deposition. Different approaches have been implemented to achieve green-yellow emission: high indium concentration (≥ 20%) with low InGaN QW thickness (< 3 nm) or vice versa. Moreover, the effect of a capping layer on top of the QWs has also been investigated. Atomic force microscopy, X-ray diffraction, room temperature photoluminescence (RTPL) and mainly transmission electron microscopy (TEM) techniques have been used to characterize these structures. The QW thicknesses and indium compositions have been determined by digital processing of lattice fringes in cross-sectional high resolution TEM images. An original treatment has been developed to analyze quantitatively InGaN QW thickness fluctuations. The structural analysis of multiple QWs with high indium composition has shown that structural defects are created in the QWs. The nature and the density of these defects have been determined and different mechanisms for their formation have been proposed. It has also been shown that a few monolayers of AlGaN or GaN capping layers deposited at the InGaN QW growth temperature prohibited indium evaporation and/or diffusion. It therefore helps to extend the emission wavelength with a reduced degradation of the RTPL efficiency. My work offers a few ways to obtain a good compromise between the conflicting parameters that govern the efficiency of QWs emitting in the green-yellow spectrum range.

Orientador: Marcelo Giannini / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-27T18:34:59Z (GMT). No. of bitstreams: 1 Vermelho_PauloMoreira_D.pdf: 2479320 bytes, checksum: 0d9cc50e5276a8b6e9a933c7dcd3239c (MD5) Previous issue date: 2015 / Resumo: Os objetivos deste estudo foram analisar as características ultramorfológicas da interface de união dente-resina, a resistência de união ao esmalte e dentina pelo método da microtração e os padrões de fratura dos espécimes testados. Dois adesivos "universais ou multi-molde" (Scotchbond Universal, 3M ESPE e All-Bond Universal, Bisco) foram testados nos modos autocondicionantes e com condicionamento prévio e comparados aos métodos tradicionais de união ao esmalte e dentina (grupos controles) utilizando os adesivos Optibond FL (Kerr) e Clearfil SE Bond (Kuraray Noritake). Esmalte e dentina de terceiros molares humanos foram utilizados nos procedimentos adesivos, os quais foram realizados com as instruções dos fabricantes. Após a aplicação dos adesivos, um bloco de compósito foi construído em incrementos. Os dentes foram seccionados longitudinalmente para obtenção de espécimes em formato de "palitos" para o ensaio de resistência de união por microtração (n=8) e as análises em microscopia eletrônica de transmissão (MET) (n=2). Os espécimes foram testados após 24 horas ou um ano de armazenamento em saliva artificial. Para a MET, solução traçadora de nitrato de prata foi utilizada para mostrar espaços nanométricos e evidências de degradação na área de união. As superfícies fraturadas dos espécimes foram observadas em microscopia eletrônica de varredura e os dados de resistência de união analisadas pela ANOVA três-fatores, teste de Tukey e Dunnett (5%). O condicionamento prévio do esmalte aumentou a resistência de união dos adesivos universais, mas essa reduziu após o armazenamento por um ano. Os adesivos universais mostraram menor resistência de união em esmalte que o grupo controle quando utilizados no modo autocondicionante no tempo de 24 horas. Nenhuma diferença significativa foi encontrada na resistência de união em dentina nos dois tempos de avaliação quando comparados aos adesivos universais e os controle. O armazenamento por um ano reduziu a resistência de união em dentina apenas para um adesivo universal usando no modo autocondicionante. A análise fractográfica em esmalte mostrou predomínio de fraturas mistas e coesivas na camada de adesivo. Em dentina, o predomínio foram fraturas mistas, adesivas e coesivas em compósito. A observação da ultramorfologia em MET mostrou a formação de hibridização e zonas de interação entre todos os adesivos em esmalte e dentina nos dois modos de aplicação. Sinais de nanoinfiltração foram identificados na área de união dentina-resina para os adesivos Scotchbond Universal e Clearfil SE Bond após armazenamento por um ano. Os resultados sugerem que armazenamento por um ano pode reduzir a resistência de união quando os adesivos universais foram aplicados em esmalte condicionado, mas em dentina condicionada não houve redução da resistência de união, exceto para o adesivo Scotchbond Universal. No esmalte a resistência de união do grupo controle foi maior que a dos adesivos universais no modo autocondicionante. Após o armazenamento por um ano, a resistência de união dos adesivos universais em esmalte tratado com ácido fosfórico não diferiu do grupo controle. Em dentina, não foi encontrada diferença significativa entre adesivos universais e os grupos controles, independente do modo de condicionamento / Abstract: The aims of this study were to analyze the ultramorphological characteristics of tooth¿resin interfaces, the microtensile bond strength of multimode adhesive systems bonded to enamel and dentin, and the failure pattern of tested specimens. Two multimode adhesives (Scotchbond Universal, 3M ESPE; All-Bond Universal, Bisco) were tested in both self-etch and etch-and-rinse modes and compared to control groups using traditional bonding techniques (Optibond FL, Kerr; Clearfil SE Bond, Kuraray Noritake) in enamel and dentin. Enamel and dentin from third human molars were used for bonding and adhesives used according to the manufacturer¿ instructions. A composite resin block was incrementally applied to bonded surfaces, and teeth were sectioned transversely to the tooth-composite interface to obtain specimens for microtensile bond strength (n=8) and transmission electron microscopy (TEM) analysis (n=2). Specimens were tested after storage for either 24 hours or 1 year in artificial saliva. For TEM, a silver tracer solution was used to reveal nanometer-sized spaces and evidence of degradation within resin¿dentin interfaces. Fractured surfaces of tested specimens were analyzed under scanning electron microscopy. Bond strength data were analyzed by three-way ANOVA and by Tukey¿s and Dunnett¿s tests (?=5%). The acid-etching mode increased the enamel bond strength of multimode adhesives; however, bond strength decreased after storage for 1 year. Multimode adhesives showed lower enamel bond strength than the control group adhesive when used in self-etch mode for 24 hours. No significant differences in dentin bond strength were noted between multimode and control adhesives in either evaluation period. Storage for 1 year only reduced the dentin bond strength for a multimode adhesive used in self-etch mode. Mixed and cohesive-within-adhesive-layer failures were predominant in enamel. In dentin most fractures were mixed, adhesive along the dentin or enamel, and cohesive within the composite layer. TEM analysis identified hybridization and interaction zones in dentin and enamel for all adhesives and application modes. Silver impregnation was detected on dentin¿resin interfaces after storage of specimens for 1 year only with the Scotchbond Universal and Clearfil SE Bond samples. Results suggested that storage for 1 year can reduce bond strength when multimode adhesives are applied on an etched surface, but the dentin bond strength was not affected when using the etch-and-rinse mode (except for the Scotchbond Universal sample). The enamel bond strengths of the control group adhesives were higher than those obtained for multimode adhesives in the self-etch mode. After storage for 1 year, the bond strengths of multimode adhesives in etched enamel did not differ from those of the control group adhesive. In dentin, no significant difference was noted between the multimode and control group adhesives, regardless of etching mode / Doutorado / Dentística / Doutor em Clínica Odontológica

Le contexte industriel actuel, animé d'un désir de prolonger la durée de fonctionnement des Réacteurs à Eau Pressurisée (REP) jusqu'à des durées de 60 ans, nécessite la compréhension de l'évolution de la microstructure et notamment d'un éventuel gonflement en conditions REP. Deux nuances de 304 (haut et bas carbone), représentatives des internes inférieurs de REP, ont été irradiées aux ions depuis les faibles doses jusqu'à des doses supérieures à la centaine de dpa, à 450°C (proche des conditions REP par la prise en compte d’un décalage flux/température), ainsi qu'à une dose intermédiaire à plus haute température 550°C. Sur la base des résultats expérimentaux des modélisations par dynamique d’amas avec le code CRESCENDO ont été réalisées afin d’étudier l’évolution de la microstructure.Les microstructures de boucles de Frank, du réseau de dislocations, des cavités et de la précipitation ont été caractérisées par Microscopie Électronique en Transmission (MET) à chacune des doses et par Sonde Atomique Tomographique (SAT) à 100 dpa. À 450°C, les conditions d’irradiations conduisent à une saturation du réseau de dislocations et des boucles de Frank, les cavités sont en faible densité induisant une fraction volumique faible (<0,1%) même dans la nuance bas carbone plus sensible au gonflement. La précipitation observée est principalement composée de carbures. En plus de l’évolution avec la dose, cette étude a permis d’analyser les effets de températures, de composition chimique et d’irradiation aux ions.Un jeu de paramètres d’entrée permettant de modéliser l’évolution de la microstructure avec la dose et le long du profil de dommage a été établi. Par modélisation il a été étudié les effets des interstitiels injectés, de la surface d’irradiation ou de la modification de l’efficacité des cascades avec la profondeur d’irradiation. / The French nuclear industry is looking into the extension of the operation time of pressurized water reactors (PWR) up to 60 years. This implies a good comprehension of the microstructural evolution under irradiation in Pressurized Water Reactors’ conditions.Two representatives stainless steels from PWR’s internals, 304 type steels, which differ in carbon content, has been irradiated form low to high doses (more than 100 dpa) at 450°C, irradiation at a second temperature (550°C) has also been performed at an intermediate dose. The choice of the temperature (450°C) was motivated by considering a temperature shift between neutron and ion irradiations due to their large difference in term of dose rate.The microstructural evolution has been characterized by transmitted electron microscopy on each conditions and by atom probe on highest irradiated samples. And modelling of the microstructure was performed using cluster dynamics code CRESCENDO.For both steels, at 450°C the dislocation network and Frank loops reach a saturation regime. As the cavity size and density are low the volume fraction is also low, even in the low carbon content steels, which is more favorable to swelling. The precipitation is mainly carbides. The effects of temperature, chemical composition and of ion irradiation were also investigated.Based on experimental results, a set of parameters which reproduces the evolution of the microstructure in respect to the dose and the depth of observation has been established. It has allowed to understand the effects of the irradiated surface, the injected interstitials and a possible evolution of the cascade efficiency along the damage profile.

TiAlN and TiAlN-based coatings that are used of relevance as protection of cutting tool inserts used in metal machining have been studied. All coatings were deposited by reactive cathodic arc evaporation using industrial scale deposition systems. The metal content of the coatings was varied by using different combinations of compound cathodes. The as-deposited coatings were temperature annealed at ambient pressure and in some cases also at high pressure. The resulting microstructure was first evaluated through a combination of x-ray diffraction and transmission electron microscopy. In addition, mechanical properties such as hardness by nanoindentation were also reported. TiAlN coatings with two different compositions were deposited on polycrystalline boron nitride substrates and then high pressure high temperature treated in a BELT press at constant 5.35 GPa and at 1050 and 1300 °C for different times. For high pressure high temperature treated TiAlN it has been shown that the decomposition is slower at higher pressure compared to ambeint pressure and that no chemical interaction takes place between TiAlN and polycrystalline cubic boron nitride during the experiments. It is concluded that this film has the potential to protect a polycrystalline cubic boron nitride substrate during metal machining due to a high chemical integrity. TiZrAlN coatings with different predicted driving forces for spinodal decomposition were furthermore annealed at different temperatures. For this material system it has been shown that for Zr-poor compositions the tendency for phase separation between ZrN and AlN is strong at elevated temperatures and that after spinodal decomposition stable TiZrN is formed.

Correlative light and electron microscopy (CLEM) is a powerful approach to investigate the molecular ultrastructure of labeled cell compartments. However, quantitative CLEM studies are rare, mainly due to small sample sizes and the sensitivity of fluorescent proteins to strong fixatives and contrasting reagents for EM. Here, we show that fusion of a self-labeling protein to insulin allows for the quantification of age-distinct insulin granule pools in pancreatic beta cells by a combination of super resolution and transmission electron microscopy on Tokuyasu cryosections. In contrast to fluorescent proteins like GFP organic dyes covalently bound to self-labeling proteins retain their fluorescence also in epoxy resin following high pressure freezing and freeze substitution, or remarkably even after strong chemical fixation. This enables for the assessment of age-defined granule morphology and degradation. Finally, we demonstrate that this CLEM protocol is highly versatile, being suitable for single and dual fluorescent labeling and detection of different proteins with optimal ultrastructure preservation and contrast.