Cette thèse a pour objectif d’apporter des informations quantitatives sur la mobilité de l’hélium dans des céramiques nucléaires avancées comme TiC, TiN et ZrC, soumises à des traitements thermiques ou bien en présence de dommages d’irradiation. L’approche expérimentale développée au cours de ce travail est basée sur l’implantation ionique d’ions d’hélium-3 de 3 MeV en profondeur dans les trois matériaux précédemment cités et sur la mesure du profil de concentration en profondeur de l’isotope 3He au moyen d’une réaction nucléaire spécifique induite par des deutérons, 3He(d, p0)4He. La microscopie électronique à transmission et la spectrométrie Raman sont couplées à l’analyse par réaction nucléaire.Parmi les principaux résultats obtenus :- aucun relâchement d’hélium n’est observé à température ambiante pour les trois composés. Les valeurs d’énergie d’activation associée au relâchement d’hélium après un recuit thermique dans l’intervalle 1100 – 1600°C sont comprises entre 0,77 et 1,2 eV et semblent étroitement liées à la microstructure initiale du composé (stoéchiométrie et taille de grains). La capacité de rétention de l’hélium-3 dans des carbures ou nitrures de métaux de transition soumis à des traitements thermiques en conditions contrôlées croît dans l’ordre ZrC < TiC < TiN.- la formation de blisters n’et observée qu’à la surface de ZrC.- les profils d’implantation d’hélium présentent deux composantes pour les trois matériaux, l’une située au voisinage de la fin de parcours des ions et la seconde plus proche de la surface. Cette dernière résulte probablement du piégeage d’atomes d’hélium par les lacunes natives présentes.- les valeurs obtenues pour le coefficient apparent de diffusion de l’hélium varient dans l’intervalle 3,58E-19 – 5,296E-18 m^2s^-1 pour TiN et 4,20E-18 – 2,59E-17 m^2s^-1 pour TiC.Les valeurs correspondantes obtenues pour l’énergie d’activation sont respectivement de 2,50 eV pour TiC et de 1,05 eV pour TiN. Le mécanisme impliqué repose sur une dissociation des amas atomes d’hélium – lacunes au voisinage de la fin de parcours des ions. Plus en surface, la diffusion est plutôt du type substitutionnel.- l’observation au MET de sections transverses de TiN préparées par la technique FIB révèlent la présence de bulles d’hélium dès recuit à 1100°C et montrent la croissance des bulles avec la température. L’énergie d’activation de croissance des bulles a été estimée à 0,38 eV. A partir de 1400°C, cette croissance résulte vraisemblablement de l’absorption de lacunes par les amas.- la pression interne des bulles a été calculée à l’aide du modèle de Trinkaus, et nous avons montré qu’à partir de 1500°C, cette pression tendait à s’approcher de la valeur du module de cisaillement de TiN (240 GPa) et qu’elle atteignait la pression d’équilibre de 2 GPa à 1600°C.- à 1100°C, il semble que la densité des bulles présentes dans TiN varie linéairement avec la fluence d’implantation. A 1500°C, la taille des bulles est d’autant plus grande que la fluence est faible.- pour ZrC, l’effet de la fluence sur la mobilité de l’hélium est comparable à celui observé pour TiN. A la plus basse fluence, le relâchement d’hélium est très faible. Il croît avec la température de recuit et avec la fluence d’implantation.- la pré-Irradiation des trois composés par des auto-Ions avant implantation d’hélium provoque une augmentation de la dureté au moins =jusqu’à une dose de 27 dpa. Une très faible augmentation du paramètre de maille est alors détectée (≤ 0.5%).- dans le cas de ces matériaux non amorphisables sous irradiation aux ions, le recuit par perte d’énergie électronique ou bien le pré-Endommagement balistique ne jouent a priori aucun rôle sur la mobilité de l’hélium, étudiée sous l’angle d’une activation thermique. / While the current second and third generation nuclear plant designs provides an economically, technically, and publicly acceptable electricity supply in many markets, further advances in nuclear energy system design can broaden the opportunities for the use of nuclear energy. The fourth generation of nuclear reactors is under development. These new reactors are designed with the following objective in mind: sustainability, safety and reliability, economics, proliferation resistance. Out of six Generation IV systems namely, Gas-Cooled Fast Reactor (GFR), Lead-Cooled fast reactor (LFR), Molten Salt Reactor (MSR), Sodium-Cooled Fast Reactor (SFR), Supercritical-Water-Cooled Reactor (SCWR), Very-High-Temperature Reactor (VHTR), this work is dedicated to identify specific fuel type that is compatible with gas-Cooled fast reactor (GFR) in-Core service conditions and could be extended to diagnose potential cladding material for SFR. The French strategy is mainly oriented towards the development of sodium-Cooled fast reactors (SFR) and very slightly focused on GFR. This dissertation is focused on the study of transition metal ceramics which are candidates for fuel coatings in GFR and have been considered as potential cladding materials for SFR. The specific fuel type in GFR should consists of spherical fuel particle made up of UC or UN, surrounded by a ceramic coating which provides structural integrity and containment of fission products. The most promising candidates for ceramic coatings are ZrN, ZrC, TiN, TiC & SiC due to a combination of neutronic performance, thermal properties, chemical behavior, crystal structure, and physical properties. It is obvious that these ceramics would be exposed to energetic fission products from fuel such as heavy ions and neutrons. These high-Energy neutron will knock the atoms in the surrounding materials and can induce (n, α) reactions, thus producing high concentration of helium atoms during and after reactor operation. The helium atoms produced are energetic and can easily penetrate into the surrounding material. Helium atoms are considered to be highly insoluble in previously studied structural nuclear materials. The accumulation of helium into solid matrix, can lead to the formation of bubbles, cavity, swelling, embrittlement etc. Helium can strongly induce grain boundary cavitation that can produce formation of inter-Granular channels, which may serve as pathways for release of radioactive elements to the environment or lead to grain-Boundary weakening and de-Cohesion. Particularly in ceramics, large quantities of helium can also lead to dimensional changes and cracks due to over-Pressurized helium bubbles. Therefore, study of helium behavior in advanced nuclear ceramics under high operating temperatures and extreme radiation conditions predicted for GFRs is viewed as crucial. In this thesis, ion-Implantation technique and material characterization techniques are used to study diffusion of helium in transition metal ceramics under thermal and extreme irradiation environments. Our main aim during this thesis is: 1) To calculate diffusion and migration energies of helium under different experimental conditions by applying theoretical models on experimental data.2) To investigate the role of microstructure such as grain boundaries, native vacancies and porosity on helium accumulation and its evolution after helium accumulation.3) To know the role of helium introduction conditions on helium diffusion. 4) To establish and validate an approach to calculate pressure built by helium gas inside the bubbles and to verify if the pressure approaches mechanical stability limit.

Este estudo longitudinal investigou a influência de tratamentos de superfície com o laser de Er:YAG com 50?s de largura de pulso sobre a adesão de dois sistemas adesivos autocondicionantes (SA) em dentina hígida (DH) e dentina afetada por cárie (DAC) através dos teste de resistência de união (RU) de microcisalhamento (?SBS), teste de ultramicrodureza da camada de adesivo (NdA) e da camada híbrida (NdCH), além de análise da interface adesiva com microscopia eletrônica de varredura (MEV). A análise qualitativa dos tratamentos de superfície realizados foi executada através de MEV e microscopia eletrônica de transmissão (MET). A dentina oclusal planificada de 215 molares humanos foi protegida com verniz ácido resistente, exceto em janela de 4x5mm para produção de DAC artificial após 7 dias de desafio cariogênico com biofilme de S. mutans, permitindo dados pareados por substrato. Os espécimes foram divididos nos grupos experimentais de acordo com: tratamento de superfície [controle-sem tratamento-(G1); Laser 80-80mJ, 2 Hz, 12.58J/cm2-(G2); Laser 50-50mJ, 10 Hz, 9.4J/cm2-(G3)]; sistema adesivo [Clearfil SE Bond(CF) e Single Bond Universal(SB)]; substrato [DH(h) ou DAC(a)] e tempo de armazenamento em saliva artificial [24 horas (24) ou 1 ano (1)], compondo 24 grupos experimentais: CFG1h24; CFG1h1; CFG1a24; CFG1a1; CFG2h24; CFG2h1; CFG2a24; CFG2a1; CFG3h24; CFG3h1; CFG3a24; CFG3a1; SBG1h24; SBG1h1; SBG1a24; SBG1a1; SBG2h24; SBG2h1; SBG2a24; SBG2a1; SBG3h24; SBG3h1; SBG3a24; SBG3a1. Nos grupos tratados com laser a largura temporal de pulso foi ajustada em 50?s. A resina composta Z350XT foi utilizada para a confecção dos corpos de prova. Os sistemas adesivos foram aplicados de acordo com as instruções do fabricante. As análises de MEV e MET de superfície avaliaram somente o efeito dos tratamentos em ambos os substratos testados. Os valores de RU e de nanodureza foram analisados através do teste de ANOVA (três fatores) e do teste de comparações múltiplas de Tukey (?=0,05). Para o teste de ?SBS, para ambos os SA, e todos tratamentos de superfície, a DAC apresentou valores de RU menores comparados à DH; a influência do armazenamento em saliva artificial foi substrato dependente: corpos de prova obtidos com DAC apresentaram queda nos valores de RU após 1 ano de armazenamento, enquanto nenhuma diferença entre os grupos experimentais foi observada em dentina hígida. NdA revelou que apenas os corpos de prova construídos com CF apresentaram redução dos valores após 1 ano. A NdCH obtida com CF e SB, resultou em menores valores em DAC comparada à DH, após 1 ano de armazenamento ambos os substratos apresentaram redução da NdCH, para todos tratamentos de superfície. A MEV revelou que todas as interfaces adesivas, especialmente aquelas obtidas em DAC, sofreram degradação intensa após 1 ano. Os tratamentos com Laser 80 e Laser 50 promovem alteração superficial característica de ablação em DAC e DH, conforme observado em MEV de superfície, e alterações de fibrilas colágenas observadas em MET. Independentemente dos SA, a adesão e nanodureza em DAC é menor que em DH. Todas as interfaces adesivas obtidas foram sensíveis ao armazenamento em saliva artificial por 1 ano. A adesão não foi influenciada pelo tratamento com o laser Er:YAG com 50?s de largura de pulso. / This longitudinal study investigated the influence of super short pulse Er:YAG laser treatment on microshear bond strength (?SBS), adhesive and hybrid layer nanohardness test and qualitative interface scanning electron microscopy (SEM) of two self-etch adhesive systems to sound (SD) and caries-affected like dentin (CAD). Additionally, qualitative investigation of surface treatments by SEM and transmission electron microscopy (TEM) were performed. CAD lesions (4x5mm) were produced by 7 days S. mutans biofilm cariogenic challenge in 215 human ground flat human dentin specimens, enabling paired data by substrate. Specimen were divided in groups according to surface treatment [control-no treatment-(G1); Laser 80-80mJ, 2Hz, 12.58J/cm2-(G2); Laser 50-50mJ, 10Hz, 9.4J/cm2-(G3)]; self-etching adhesive system [Clearfil SE Bond(CF) and Single Bond Universal(SB)]; substrate [SD(h) or CAD(a)] and artificial saliva storage [24 hours(24) or 1 year(1)]: CFG1h24; CFG1h1; CFG1a24; CFG1a1; CFG2h24; CFG2h1; CFG2a24; CFG2a1; CFG3h24; CFG3h1; CFG3a24; CFG3a1; SBG1h24; SBG1h1; SBG1a24; SBG1a1; SBG2h24; SBG2h1; SBG2a24; SBG2a1; SBG3h24; SBG3h1; SBG3a24; SBG3a1. Pulse duration was set in 50?s for laser groups. ?SBS, nanohardness and interface SEM specimen preparation was constructed with Z350XT composite resin. Adhesive systems were applied according to manufacturer\'s instructions. Surface SEM and TEM specimen only evaluated treatment effects on distinct substrates. The ?SBS and nanohardness means were analysed using three-way ANOVA and Tukey´s multiples comparisons test (?=0.05). For ?SBS test, for both adhesive systems, and all surface treatments, CAD revealed lower ?SBS values compared to SD; the influence of artificial saliva storage was substrate dependent. CAD specimens resulted in lower ?SBS values after 1 year, while no difference among experimental groups was observed in SD. The adhesive layer (AL) nanohardness statistical evaluation revealed that only CF specimens decreased the AL nanohardness after 1 year of storage. The hybrid layer (HL) produced with CF and SB, resulted in lower nanohardness values for CAD than SD, which reduces after 1 year storage, for all surface treatments. Interface SEM analysis revealed that all adhesive interfaces, especially those in CAD, have experienced degradation after 1 year of storage. Laser 80 and Laser 50 promotes surface ablation characteristics in CAD and SD, as noted in surface SEM and collagen fibrils alterations observed in TEM. Despite of adhesive systems, bonding and nanohardness to CAD is lower than to SD. All tested adhesive interfaces were sensitive to saliva storage. Surface treatment with 50?s Er:YAG laser did not influence on bonding.

Die untersuchten Ferekristalle sind neuartige Verwachsungs-Schichtverbindungen aus m Monolagen von Niobdiselenid (NbSe2), die wiederholt mit n atomaren Bilagen von Bleiselenid (PbSe) oder Zinnselenid (SnSe) geschichtet sind. Niobdiselenid als Volumenmaterial besitzt eine Schichtstruktur und ist ein Supraleiter. Aufgrund ihrer gezielt einstellbaren atomar geschichteten Struktur können Ferekristalle als Modellsysteme für geschichtete Supraleiter dienen. In dieser Arbeit werden ihre strukturellen und elektrischen Eigenschaften untersucht. Mittels Transmissionselektronenmikroskopie wird ihre turbostratisch ungeordnete, nanokristalline Struktur nachgewiesen. Die atomare Struktur innerhalb der einzelnen Schichten ist ähnlich wie in den Volumenmaterialien NbSe2, PbSe und SnSe, wobei die kristallographischen c-Achsen parallel zur Stapelrichtung der Ferekristalle zeigen. Eine quantitative Analyse unter Verwendung eines Zwei-Schicht-Modells für den spezifischen Widerstand, Hall-Koeffizienten und Magnetwiderstand liefert ähnliche Ladungsträgersorten, -dichten und –beweglichkeiten in den NbSe2-Schichten, wie sie für isolierte Einzellagen von NbSe2 berichtet wurden. Diese unterscheiden sich von denen des Volumenmaterials NbSe2. Erstmals wurde ein Übergang der Ferekristalle in den supraleitenden Zustand nachgewiesen. Die Sprungtemperaturen sind dabei in etwa auf die Hälfte der Sprungtemperaturen der jeweiligen nicht turbostratisch ungeordneten Misfit-Schichtverbindungen reduziert. Diese Reduzierung kann der turbostratischen Unordnung der Ferekristalle zugeordnet werden. Das Verhältnis zwischen der schichtsenkrechten Ginzburg-Landau-Kohärenzlänge und dem Abstand zwischen den supraleitenden Schichten ist bei den Ferekristallen kleiner als bei den nicht ungeordneten Misfit-Schichtverbindungen, was Ferekristalle zu vielversprechenden Kandidaten für (quasi-)zweidimensionale Supraleiter macht. / The investigated ferecrystals are novel layered intergrowth compounds consisting of m monolayers of niobium diselenide (NbSe2) stacked repeatedly with n atomic bilayers of lead selenide (PbSe) or tin selenide (SnSe). Bulk NbSe2 is a layered compound showing superconductivity. Due to their artificially atomic-scale layered structure, which is tunable on the atomic scale, ferecrystals can serve as model systems for layered superconductors. In this study, their structural and electrical properties are investigated. Using transmission electron microscopy their turbostratically disordered, nanocrystalline structure is revealed. The atomic structure within the individual layers is similar as for bulk NbSe2, PbSe and SnSe, with the crystallographic c-axes parallel to the stacking direction in the ferecrystals. A quantitative analysis using a two-layer model fit for the electrical resistivity, Hall coefficient and magnetoresistance yields a similar carrier type, density and mobility in the NbSe2 layers as reported for isolated NbSe2 monolayers. These values differ from those of bulk NbSe2. For the first time, a normal-to-superconducting transition has been detected in ferecrystals. The transition temperatures of the ferecrystals are reduced to about a half of those of analogous non-disordered misfit layer compounds. This reduction in transition temperature can be correlated to the turbostratic disorder in ferecrystals. The ratio between the cross-plane Ginzburg-Landau coherence length and the cross-plane distance between the NbSe2 layers for the ferecrystals is lower than for non-disordered misfit layer compounds, making ferecrystals promising candidates for (quasi-)two-dimensional superconductors.

A terapia de fotobiomodulação (PBMT do inglês photobiomodulation therapy) exerce efeitos benéficos em processos relevantes para a regeneração tecidual. A técnica de membranas celulares (CSs; cell sheets) pode gerar grande quantidade de células organizadas em uma matriz extracelular (MEC) produzida por essas células. A constituição de MEC das CSs pode ser de importância para a regeneração de tecidos. O colágeno tipo I, a fibronectina e a tenascina são proteínas da MEC já detectadas em CSs de células-tronco da polpa dentária humana. O objetivo deste estudo foi investigar os efeitos de diferentes parâmetros de PBMT sobre a arquitetura (histologia), composição proteica (Western blotting e imunoistoquímica) e ultraestrutura (MEV e MET) da MEC de CSs de células-tronco da polpa dental humana. As células-tronco foram descongeladas e recaracterizadas através da análise de seu perfil imunofenotípico avaliado pela expressão de moléculas de superfície utilizando citometria de fluxo para marcadores associados a células-tronco mesenquimais (MSC do inglês mesenchymal stem cells; CD105, CD146 e CD44) e não associados (CD45, CD34 e CD14). As CSs foram formadas em placas de cultivo celular após 15 dias em cultura em meio clonogênico suplementado com vitamina C (20 ?g/ml). As culturas celulares foram alocadas em 3 grupos experimentais diferentes, como segue: Controle: nenhum tratamento adicional; PBMT1 e PBMT2. A PBMT foi realizada com um laser diodo vermelho contínuo, aplicando-se os seguintes parâmetros gerais: 660nm, 20mW, 0,028cm2 e 0,71W/cm2. Os parâmetros do PBMT1 foram: 4s, 3J/cm2 e 0,08J por ponto, e o PBMT2: 7s, 5J/cm2 e 0,14J por ponto. As irradiações foram realizadas em dias alternados durante todo o período do experimento, em modo pontual (5 pontos / poço ou 13 por placas de 100 mm de diâmetro) em contato com a base da placa. Após a formação das CSs, 15 dias após o plaqueamento, estas foram submetidas a análises histológica, imunoistoquímica, Western blotting, microscopia eletrônica de transmissão e de varredura. Comparações estatísticas foram realizadas (p <0,05). As células apresentaram perfil imunofenotípico clássico de MSCs, mostrando a expressão de marcadores associados a MSCs, enquanto a expressão dos marcadores não associados a MSCs estavam ausentes. O colágeno tipo I, colágeno tipo III e fibronectina estavam presentes no MEC das CSs. Western blotting revelou maior síntese de fibronectina nas CSs submetidas ao PBMT1. A ultraestrutura geral dos CSs foi diversa nos 3 grupos experimentais. As CSs do grupo PBMT1 apresentaram aspecto epitelióide, enquanto no grupo PBMT2 as CSs apresentaram células isoladas e fusiformes dispostas em feixes unidirecionais. MET identificou uma MEC mais madura e sinais de apoptose nos grupos submetidos à PBMT. A PBMT influenciou a composição e ultraestrutura da MEC de CSs de células-tronco da polpa dentária. Assim, a PBMT pode ser importante na determinação da qualidade mecânica das CSs, o que pode favorecer a terapia celular, facilitando o transplante das células-tronco. / Photobiomodulation therapy (PBMT) improves processes relevant to tissue regeneration. The technique of cell sheets (CSs) can generate large amount of cells organized in an extracellular matrix (ECM) produced by these cells. The constitution of the ECM of CSs could be of importance for tissue regeneration. Type I collagen, fibronectin and tenascin are ECM proteins already detected in CSs of human dental pulp stem cells. The aim of this study was to investigate the effects of different PBMT parameters on the architecture (histology), protein composition (Western blotting and immunohistochemistry) and ultrastructure (SEM and MET) of the MEC of CSs of human dental pulp stem cells. Dental pulp stem cells were thawed and recharacterized by the expression profile of the surface molecules using flow cytometry for mesenchymal stem cells (MSC) -associated (CD105, CD146 and CD44,) and non associated (CD45, CD34 and CD14) markers. The CSs were formed in cell culture plates after 15 days in culture in clonogenic medium supplemented with vitamin C (20 ?g/ml). The cell cultures were allocated in 3 different experimental groups, as follows: Control: no further treatment; PBMT1 and PBMT2. PBMT was performed with CW red diode laser applying the following general parameters: 660nm, 20mW, 0.028cm2 spot size and 0.71W/cm2. The PBMT1 parameters were: 4s, 3J/cm2 and 0.08J per point, and the PBMT2: 7s, 5J/cm2, and 0.14J per point. The irradiations were done on alternate days throughout the experimental time, in a punctual mode (5 points/well or 13 points/100mm-diameter dishes) in contact at the base of the plate. After the CSs formation, 15 days after plating, they were submitted to histology, immunohistochemistry, Western blotting, transmission electron microscopy and scanning electron microscopy analyses. Statistical comparisons were performed (p<0.05). The cells presented the classical immunoprofile of MSCs showing the expression of MSCs-associated markers, whereas the expression of the MSCs non-associated markers were absent. The type I collagen, type III collagen and fibronectin were present in the MEC of the CSs. Western blotting revealed a higher amount of fibronectin in the CSs submitted to PBMT1. The overall ultrastructure of the CSs was diverse in the 3 experimental groups. PBMT1 leads to epithelial-like CS, whereas the PBMT2 leads to a CSs with isolated fusiform cells arranged in unidirectional bundles. MET identified a more mature ECM and signs of apoptosis in the PBMT groups. PBMT may influence the composition and ultrastructure of the ECM of CSs of dental pulp stem cells. Thus, PBMT could be of importance in the determination of the mechanical quality of CSs, which may favor cell therapy by improving the CS transplantation approach.

In dieser Arbeit untersuchen wir die grundlegenden Wachstums- und Relaxationsprozesse, die es erlauben den Verzerrungszustand von GaN (0001) beim Wachstum auf Silizium (111) Substraten einzustellen und die resultierende Dichte an Durchstoßversetzungen zu reduzieren. Zu deren Analyse werden GaN (0001) Schichten, die mittels metallorganischer Gasphasenepitaxy abgeschieden worden sind, hauptsächlich mit transmissionselekronenmikroskopischen Methoden untersucht. Die wesentlichen Erkenntnisse der Arbeit sind: (i) Der Aufbau einer kompressiven Verzerrung von GaN (0001) Filmen mittels AlGaN Zwischenschichten beruht auf einer Asymmetrie der plastischen Relaxation an den beiden Grenzflächen der AlGaN Zwischenschicht. Fehlpassungsversetzungen bilden sich zwar an beiden Grenzflächen aus, jedoch ist der mittlere Abstand zwischen Versetzungslinien an der unteren Grenzfläche kleiner, als an der oberen. (ii) Plastische Relaxation von verzerrten (0001) Wurtzit Schichten erfolgt im Wesentlichen durch Bildung von a-Typ Fehlpassungsversetzungen im 1/3 |{0001} Gleitsystem. Diese bilden sich aber nur dann, wenn die verzerrten Schichten eine 3-D Morphologie aufweisen. Eine quantitative Modellierung dieses Prozesses zeigt, dass die kritische Schichtdicke für das Einsetzen der plastischen Relaxation wesentlich vom Wachstumsmodus bestimmt wird. (iii) Eine Silizium Delta-Dotierung der GaN (0001) Oberfläche führt zum Wachstum einer kohärenten Sub-Monolage SiGaN3, die eine periodisch Anordnung von Silizium- und Galliumatomen, sowie Galliumvakanzen aufweist. Da das Wachstum von GaN direkt auf der SiGaN3-Monolage unterdrückt ist, tritt ein Übergang zu 3-D Inselwachstum auf, das zunächst ausschließlich in Löchern der SiGaN3-Monolage anfängt. Eine hohe Konzentration von Silizium auf der GaN (0001) Oberfläche wirkt also als Anti-Surfactant beim epitaktischen Wachstum von GaN. Rechnungen mittels der Dichtefunktionaltheorie liefern Erklärungen für das beobachtete Wachstumsverhalten. / In this work we study the basic growth and relaxation processes that are used for strain and dislocation engineering in the growth of GaN (0001) films on silicon (111) substrates. To analyse these processes, samples, grown by metalorganic vapour phase epitaxy were investigate by means of transmission electron microscopy. Our investigations have revealed the following main results: (i) Strain engineering and build-up of compressive strain in GaN (0001) films by means of AlGaN interlayer is based on an asymmetry in plastic relaxation between the two interfaces of the AlGaN interlayer. Although misfit dislocation networks form at both interfaces of the interlayer, the average spacing of dislocation lines at the lower interface is smaller than that at the upper one. (ii) Plastic relaxation of strained (0001) wurtzite films is caused mainly by formation of a-type misfit dislocations in the 1/3 |{0001} slip-system. These a-type misfit dislocations form once the strained films undergo a transition to a 3-D surface morphology, e.g. by island growth or cracking. Quantitative modelling of this process reveals that the critical thickness for nucleation of a-type misfit dislocations depends next to the lattice mismatch mainly on the growth mode of the film. (iii) Silicon delta-doping of the GaN (0001) surface leads to the growth of a coherent sub-monolayer of SiGaN3 that shows a periodic arrangement of silicon and gallium atoms and gallium vacancies. Since growth of thick GaN layers directly on top of the SiGaN3-monolayer is inhibited a transition towards 3-D island growth occurs, whereby GaN islands exclusively nucleate at openings in the SiGaN3-monolayer. A high concentration of silicon on the GaN (0001) surface thus acts as an anti-surfactant in the epitaxial growth of GaN. Our density functional theory calculations provide an explanation for both the self-limited growth of the SiGaN3-monolayer, as well as for the blocking of GaN growth on top of the SiGaN3-monolayer.

Les maladies ostéoarticulaires représentent environ 10% de l’ensemble des pathologiessurvenant en France chaque année. Les difficultés pour identifier les causes de ces maladiesproviennent pour une part d’un manque de compréhension du mécanisme de lubrificationd’une articulation synoviale saine. Dans ce contexte, un premier objectif de ce travail a été d’analyser la structurediscontinue du liquide synovial à partir de prélèvements animaux sains et de la reproduire àpartir de composants biomoléculaires commerciaux afin de comprendre le mécanisme delubrification dans le cas sain. Le deuxième objectif de cette thèse a été d’analyser l’évolution de la structure et despropriétés lubrifiantes du liquide synovial dans le stade précoce de pathologies noninflammatoiresou inflammatoires à partir de prélèvements pathologiques humains. Afind’étudier plus finement l’évolution de la lubrification pathologique cette thèse a visé àdévelopper aussi des modèles de lubrifiants obtenus à partir de cultures cellulaires desynoviocytes humains en combinant l’action de facteurs inflammatoire (cytokines).L’ensemble des résultats montre l’importance de la structure supramoléculaire duliquide synovial dans l’obtention de bonnes propriétés lubrifiantes ; cette relation devraitconstituer d’une part un paramètre clé dans le diagnostic précoce des pathologies articulaireset d’autre part une voie de développement de liquides thérapeutiques à base de lubrifiantsnanostructurés / Osteoarticular diseases account for approximately 10% of all diseases occurring inFrance each year. The difficulties in identifying their causes are also due to a deficiency inunderstanding the lubrication mechanism of healthy synovial joint.In this context, the first objective of the present study was to analyze the discontinuousstructure of synovial fluid samples from healthy animals and to reproduce it using commercialbiomolecular components in order to understand the lubrication mechanism in the healthycase. The second objective of this thesis was to analyze the evolution of the structure andthe lubricating properties of synovial fluid in the early stage of non-inflammatory andinflammatory diseases using pathological human fluid samples. In order to study moreprecisely the evolution of pathological lubrication this work aimed to develop lubricantmodels obtained from cell cultures of human synoviocytes adding the action of pathologicalinflammatory factors (cytokines). All together the results show the importance of the supramolecular structure of thesynovial fluid in obtaining good lubricating properties what may be a key parameter in theearly diagnosis of joint diseases and even more a chance to develop therapeutic fluids basedon nanostructured lubricants

Avanços na tecnologia introduziram o laser como um grande aliado na remoção seletiva do tecido cariado. Entretanto, o efeito dos lasers e seus diferentes parâmetros nos tecidos duros dentais e fibrilas colágenas não foi completamente estudado. O objetivo deste estudo foi avaliar os efeitos da irradiação com os lasers de Er:YAG e Er,Cr:YSGG na morfologia e na resistência de união da dentina irradiada à resina composta. Sessenta e quatro hemi-discos de dentina obtidos de terceiros molares humanos foram aleatoriamente divididos em 9 grupos (n=7): G1 Controle (não irradiado); G2 Laser de Er:YAG 250 mJ, 4 Hz; G3 Laser de Er:YAG 200 mJ, 4 Hz; G4 Laser de Er:YAG 180 mJ, 10 Hz; G5 Laser de Er:YAG 160 mJ, 10 Hz; G6 - Laser de Er,Cr:YSGG 2W, 20 Hz; G7 - Laser de Er,Cr:YSGG 2,5W, 20 Hz; G8 - Laser de Er,Cr:YSGG 3W, 20 Hz; G9 - Laser de Er,Cr:YSGG 4W, 20 Hz. Destes, vinte e sete amostras (n=3) foram processadas e destinadas à avaliação em Microscopia Eletrônica de Varredura (MEV) para análise morfológica de superfície e em corte transversal da dentina irradiada. Nove fragmentos (n=1) foram submetidos à Microscopia Eletrônica de Transmissão (MET) e vinte e sete (n=3) foram restaurados para análise da interface adesiva. Para o teste de resistência de união, 45 superfícies dentinárias planificadas foram restauradas e, após 24 horas de armazenamento em água, foram submetidas ao teste de microtração. O teste de ANOVA (=5%) foi realizado e verificou-se que o G1 apresentou os maiores valores de resistência de união quando comparado aos demais grupos experimentais. Não houve diferença estatisticamente significativa entre os grupos irradiados, e a análise morfológica revelou para estes grupos uma superfície irregular, com aparência escamosa, sem smear layer e com os túbulos dentinários abertos. Nos cortes transversais foi possível observar que esses efeitos se estendem à subsuperfície dentinária e resultam na formação de um padrão modificado dos tags durante o processo de hibridização. Os resultados deste estudo in vitro sugerem que a irradiação com os lasers de Er:YAG e Er,Cr:YSGG promovem um padrão morfológico específico da superfície dentinária, os quais podem interferir negativamente nos valores de resistência de união à resina composta. / Improvements on technology have introduced the laser as a great ally in the selected removal of dental caries. However, the different laser parameters and their effects on dental hard tissues and collagen fibrils have not yet been completely studied. The aim of the present study was to evaluate the effect of Er:YAG and Er,Cr:YSGG laser irradiation on dentin morphology and on microtensile bond strength of resin composite to the irradiated dentin. Sixty-four dentin hemi-disks obtained from sound human third molars were randomly divided into 9 groups (n=7): G1 Control, G2 Er:YAG Laser 250 mJ, 4 Hz; G3 Er:YAG Laser 200 mJ, 4 Hz; G4 Er:YAG Laser 180 mJ, 10 Hz; G5 Er:YAG Laser 160 mJ, 10 Hz; G6 - Er,Cr:YSGG Laser 2W, 20 Hz; G7 - Er,Cr:YSGG Laser 2,5W, 20 Hz; G8 - Er,Cr:YSGG Laser 3W, 20 Hz; G9 - Er,Cr:YSGG Laser 4W, 20 Hz. Twenty seven specimens (n=3) were processed for Scanning Electron Microscopy (SEM) for surface and cross-sectional morphological analysis. Nine specimens (n=1) were processed for Transmission Electron Microscopy (TEM) and twenty seven (n=3) were restored to evaluate the adhesive interface. For the microtensile bond strength (^TBS) test, 45 flat occlusal dentin surfaces were restored and after storage in water for 24h, were submitted to ^TBS test. ANOVA (=5%) showed that G1 (control group) presented the highest ^TBS values when compared with the irradiated groups, which did not differ from each other. SEM analysis showed an irregular scaly surface, free of smear layer and with open dentinal tubules. The cross-sectional dentin micrographs showed that the effects of laser extended to the dentin subsurface resulting in a pattern of tags modified in the hibridization process. The findings of this in vitro study showed that both Er:YAG and Er,Cr:YSGG laser irradiation resulted in a specific morphological pattern of dentin that negatively affects the bond strength to resin composite to such dentin.

X. fastidiosa é uma bactéria fitopatogênica limitada ao xilema, que tem afetado um grande número de plantas no Brasil e no mundo. Muitos trabalhos já foram realizados sobre esta bactéria, mas pouco se conhece a respeito da adesão, colonização e expressão dos sintomas. Os objetivos deste trabalho foram: a) através do uso da microscopia eletrônica e de luz, determinar e relacionar o número de vasos colonizados de citros, cafeeiro e ameixeira com a sintomatologia em folhas; b) estudar a adesão, migração radial e colonização dos vasos do xilema do pecíolo de folhas de citros pela bactéria; c) estudar algumas variáveis experimentais que afetam a expressão dos sintomas em fumo; d) verificar os sítios de ligação da bactéria em cigarrinhas vetores; e) estudar a adesão e a formação do biofilme por X. fastidiosa em superfície de poliestireno, como uma nova metodologia. Os resultados mostraram em ameixeira e cafeeiro uma relação entre o número de vasos colonizados e a expressão de sintomas necróticos, relação esta que não pode ser observada para citros, o qual apresentava um número de vasos colonizados do pecíolo bem menor que o das outras duas espécies. No estudo da bactéria nos vaso do xilema de citros foi possível verificar as diversas fases do processo de colonização do xilema, bem como a capacidade da bactéria em degradar a parede celular primária da pontuação e migrar para os vasos adjacentes. Neste estudo foi também possível verificar respostas da planta à bactérias caracterizadas pela produção de cristais no lúmen dos vasos do xilema e o acúmulo de goma e hiperplasia de células nas folhas. No estudo com variedades de fumo verificou-se que a cultivar Havana apresentou expressão de sintomas mais intensa que as variedades TNN e RP1 e que o aparecimento dos mesmos não foi influenciado pelo volume de inóculo e pelo local de inoculação, mas sim pela adubação com sulfato de amônio, a qual retardou o aparecimento dos sintomas e reverteu os sintomas inicias em folhas após a aplicação. Em cigarrinhas, células bacterianas com morfologia similar as de X. fastidiosa, foram visualizadas aderidas pela parte lateral na câmara do cibário (sulco longitudinal, parede lateral e membrana do diafragma) de Acrogonia citrina, e Oncometopia facialis, no canal do apodeme de Dilobopterus costalimai e pela parte polar no precibário de O. facialis. Finalmente, no estudo da adesão de X. fastidiosa a película de poliestireno, os resultados revelaram as várias fases da formação do biofilme, aspectos da sua arquitetura, e indicaram que a técnica é uma ferramenta adequada para o estudo da formação do biofilme e também da morfologia das bactérias. Os resultados são discutidos em termos de modelos de adesão e colonização, da bactéria e importância para o conhecimento dos mecanismos de patogenicidade da bactéria em plantas e transmissão pelos vetores. / X. fastidiosa is a xylem-limited bacterium that has been affecting a high number of plants in Brazil and in the world. A lot of researches were already accomplished on this bacterium, but little is known regarding the adhesion, colonization and expression of the symptoms in plants. The objectives of this work were: a) through the use of electron microscopy and of light microscopy determine and to correlate the number of xylem colonized vessels of petiole of sweet orange, coffee and plum with chlorosis and leaf scorching in leaves; b) study the adhesion, radial migration and colonization of the vessels of the petiole xylem of sweet orange by the bacterium; c) study some experimental variables that affect the expression of symptoms in tobacco; d) verify the retention sites of the bacterium in sharpshooters; d) study the adhesion and biofilm formation by X. fastidiosa on polystyrene surface. The results showed a relationship between the number of colonized vessels in plum and coffee and the expression of necrotic symptoms. However, that relationship was not observed for sweet orange, which presented a number of colonized vessels smaller than the other two species. In the study of the bacterium in the xylem vessels of sweet orange it was possible to verify the several phases of the colonization process of the xylem as well as the ability of the bacterium to degrade the primary cell wall of the pit and migrate to adjacent vessels. It was also possible to verify responses of the plant to the bacterium characterized by the production of crystals in the lumen of the xylem vessels and gum accumulation and hyperplasia in the leaf cells. Regarding the tobacco varieties it was verified that the expression of symptoms is more intense in the cultivar Havana than in the cultivars TNN and RP1. It was also seen that symptoms expression was not influenced by the inoculum volume or the inoculation place, but it was altered by fertilization with ammonium sulfate, which delayed the beginning of the symptoms and reverted the symptoms in leaves after the application. In sharpshooters, bacterial cells exhibiting morphology similar to X. fastidiosa were visualized attached to the lateral side in the cibarium camera (longitudinal, lateral wall and membrane of the diaphragm) of Acrogonia citrina, and Oncometopia facialis, in the apodemal channel of Dilobopterus costalimai, and in the polar part in the pre-cibarium of O. facialis. Finally, in the study of the adhesion of X. fastidiosa on polystyrene surface, the results revealed the several phases of biofilm formation; aspects of its architecture, and it also indicated that the technique is an appropriate tool to study of the formation of biofilms and also of the bacterial morphology. The results are discussed regarding adhesion models, colonization, and distribution of the bacterium in the plant and the importance of knowing the pathogenicity mechanisms of X. fastidiosa and its transmission by the insect vectors.

Environmentally-assisted cracking (EAC) phenomena affect the in-service behaviour of austenitic stainless steels in nuclear power plants. EAC includes such degradation phenomena as Stress Corrosion Cracking (SCC) and Corrosion Fatigue (CF). Factors affecting EAC include the material type, microstructure, environment, and stress. This is an important degradation issue for both current and Gen III+ light water reactors, particularly as nuclear power plant lifetimes are extended ( > 60 years). Thus, it is important to understand the behaviour of the alloys used in light water reactors, and phenomena such as SCC to avoid failures. Although there is no agreement on the mechanism(s) of SCC, the importance of localized electrochemical reactions at the material surface is widely recognised. Considerable research has been performed on SCC and CF crack growth, but the initiation phenomena are not fully understood. In this project, novel in situ analytical TEM techniques have been developed and applied to explore localised reactions in Type 304 austenitic stainless steel. In situ transmission electron microscopy has become an increasingly important and dynamic research area in materials science with the advent of unique microscope platforms and a range of specialized in situ specimen holders. In metals research, the ability to image and perform X-ray energy dispersive spectroscopy (XED) analyses of metals in liquids are particularly important for detailed study of the metal-environment interactions with specific microstructural features. To further facilitate such studies a special hybrid specimen preparation technique involving electropolishing and FIB extraction has been developed in this thesis to enable metal specimens to be examined in the liquid cell TEM specimen holder using both distilled H2O and H2SO4 solutions. Furthermore, a novel electrode configuration has been designed to permit the localized electrochemical measurement of electron-transparent specimens in the TEM. These novel approaches have been benchmarked by extensive ex situ experiments, including both conventional electrochemical measurements and microcell measurements. The results are discussed in terms of validation of in situ test data as well as the role of the electron beam in the experiments. In situ liquid cell TEM experiments have also explored the localized dissolution of MnS inclusions in H2O, and correlated the behaviour with ex situ experiments. Based on the research performed in this thesis, in situ liquid cell and in situ electrochemical cell experiments can be used to study nanoscale reactions pertaining to corrosion and localized dissolution leading to "precursor" events for subsequent EAC phenomena.

L'amiante est un matériau connu et utilisé par l'homme depuis près de 5000 ans, sa définition commerciale comprend six différents types de minéraux fibreux. En raison de leurs nombreuses propriétés thermiques et mécaniques, l'amiante a été exploité intensivement pour un usage industriel au cours du siècle dernier. Il est maintenant bien reconnu que l'exposition à l'amiante peut causer des dommages sévères pour la santé, son usage et exploitation sont donc bannis dans de nombreux pays et son exposition est strictement réglementée. L'application de ces divers règlements nécessite des méthodes d'analyse pour les soutenir. La microscopie électronique en transmission (MET) est l'outil le plus puissant et efficace pour l'analyse des fibres d'amiante. Des erreurs d’identifications causées par l’endommagement des fibres d'amiante peuvent cependant se produire, cette problématique a été étudiée en profondeur. Des fibres d'amiante amosite ont été initialement étudiées pour évaluer les dommages causés par le faisceau d'électrons du microscope électronique à transmission. Puisque les rapports d'intensité de rayons X élémentaires, obtenus par spectroscopie des rayons X en dispersion des énergies (EDS), sont couramment utilisés pour l'identification de l'amiante, l'impact de l’endommagement sur ces rapports a été mesuré. Il a été déterminé que le rapport magnésium/silicium était le plus sensible à l’endommagement causé par le faisceau d'électrons. Différents essais ont montré que la plupart des fibres ont un seuil de densité de courant au-dessus duquel la composition chimique de la fibre est modifiée. La valeur de ce seuil de densité de courant varie en fonction de la fibre. L'existence d'une valeur seuil de dose électronique a également été démontrée. Cette valeur est dépendante de la densité de courant utilisée, et peut être augmentée lorsqu’une période de récupération entre les expositions au faisceau d'électrons est octroyée. Cette étude a également permis d’établir que le courant du faisceau d'électrons est directement lié au taux d’endommagement au-dessus d'une densité de courant de 165 A/cm2. Des lignes directrices ont été établies afin de veiller à ce que les fibres d'amosite ne soient pas endommagées pendant l’analyse. Il a été déterminé que l'analyse doit être effectuée en dessous d'une densité de courant de 100 A/cm2. Dans la deuxième partie de cette étude, l'objectif principal était d'évaluer si la température est un facteur influençant l’endommagement des fibres d'amiante et, si oui, comment il peut être utilisé pour minimiser cet endommagement. Il a été constaté que l'abaissement de la température jusqu’à 123 K peut inhiber, pendant un temps donné, la manifestation de l’endommagement. La diminution significative de la diffusion des atomes à basse température empêche momentanément la perte de masse, ce qui réduit considérablement la possibilité d'une identification erronée des fibres d'amiante anthophyllite. Les résultats obtenus dans cette étude suggèrent fortement que le mécanisme d’endommagement prédominant est probablement lié au modèle d’endommagement par un champ électrique induit (DIEF). Dans un troisième temps, l'effet de la tension d'accélération sur l’endommagement de quatre types de fibres d'amiante différents; chrysotile, amosite, crocidolite et anthophyllite a été étudié. Les résultats démontrent que, contrairement à ce qui est généralement recommandé, il est préférable d'utiliser une tension d'accélération de 200 kV à 100 kV afin d'éviter l’endommagement. Les résultats mettent en lumière les mécanismes d'endommagement possibles; le plus prédominant semble être causé par un champ électrique induit, la radiolyse n’est toutefois pas exclue, mais semble de moindre importance et le « knock-on » est considéré comme négligeable dans les conditions utilisées. / Asbestos is a material known and used by man for nearly 5000 years, its commercial definition includes six different types of fibrous mineral. Because of their numerous thermal and mechanical properties, asbestos has been mined intensively for commercial use in the last century. It is now well recognized that asbestos exposure can cause severe damage to health and thus its use and exploitation is therefore banned in many countries and its exposure is strictly regulated. The application of those regulations requires rigorous analytical methods to support it. Transmission electron microscopy (TEM) is the most powerful and efficient tool for the analysis of asbestos fibers. However, identification errors caused by damage to asbestos fibers can occur and this problem has been investigated in depth. Asbestos amosite fibers were initially investigated to evaluate the damage caused by a transmission electron microscope electron beam. Since elemental x-ray intensity ratios obtained by energy dispersive x-ray spectroscopy (EDS) are commonly used for asbestos identification, the impact of beam damage on these ratios was measured. It was determined that the magnesium/silicon ratio was the most sensitive to damage caused by the electron beam. Various tests showed that most fibers have a current density threshold above which the chemical composition of the fiber is modified. The value of this threshold current density varied depending on the fiber. The existence of a threshold electron dose was also demonstrated. This value was dependent on the current density used and can be increased by providing a recovery period between exposures to the electron beam. This study also established that the electron beam current is directly related to the damage rate above a current density of 165 A/cm2. Guidelines were established in order to ensure that the amosite fibers are not damaged. It was determined that analysis should be conducted below a current density of 100 A/cm2. In the second part of this study, the main objective was to assess whether temperature is a factor influencing damage to asbestos fibers and, if so, how it can be used to minimize damage. It was found that lowering the temperature to 123 K can inhibit, for a given time, the manifestation of the damage. The significant decrease of atom diffusion at low temperature momentarily prevents mass loss, greatly reducing the possibility of misidentification of vi anthophyllite asbestos fibers. The results obtained in this study strongly suggest that the predominant mechanism damage is probably related to the induced-electric-field model. In a third part, the effect of the acceleration voltage on the damage of four different types of asbestos fibers; chrysotile, amosite, crocidolite and anthophyllite, was investigated. The results support the conclusion that contrary to what is usually recommended, it is best to use an acceleration voltage of 200 kV than 100 kV in order to avoid damage. The findings shed light on possible damage mechanisms; the most predominant seems to be caused by an induced electric field, radiolysis is not excluded but seems less important and knock-on is thought to be negligible for the conditions used.