Dehnungssensoren werden zur Überwachung von sicherheitsrelevanten Bauteilen, besonders in Bauteilen aus faserverstärkten Polymermatrixverbundwerkstoffen eingesetzt. Durch deren Integration in das Bauteilinnere werden sie vor schädigenden mechanischen sowie korrosiven Einwirkungen geschützt. Dies gewährleistet eine zuverlässige sowie dauerhafte Funktion. Verschiedene Ansätze zur Weiterentwicklung integrierbarer Dehnungssensoren werden international untersucht. Die Verringerung des Sensordurchmessers auf Abmaße im Bereich des Durchmessers von Verstärkungsfasern ist dabei ein bedeutendes Entwicklungsziel. Insbesondere bei der Integration in Bauteile aus faserverstärkten Kunststoffen sorgen zum Durchmesser von Fasern vergleichbare Sensordurchmesser für eine optimale Sensoranbindung. Die Bildung von Harznestern sowie schwächender Unstetigkeiten kann mittels dünner Sensoren verhindert werden. Dies gewährleistet eine artefaktefreie Dehnungsmessung. Drei verschiedene Ansätze für neuartige Dehnungssensoren mit kleinem Querschnitt wurden in dieser Arbeit untersucht. / Strain sensors are used for structural health monitoring issues, certainly in parts with high safety requirements made of fibre-reinforced plastic composites. The integration of these sensors inside the parts protects them against any mechanical and corrosive impact. The sensor functionality can be enhanced by integration. There is a lot of international research effort to further develop integratable strain sensors. Different approaches are currently pursued. This thesis presents the results of investigations on three different approaches for novel strain sensors. The main goal of these investigations was to minimise the sensor diameter down to the diameter of reinforcing fibres. The small diameter allows for an optimum and artefact free integration of the sensors. The formation of resin nests and notches to the material structure can be prevented by integrating sensor with a smaller diameter. The strain measurement and monitoring is enhanced and more reliable then.

An experimental method was further developed to quantify the anisotropy of multi-site fatigue crack initiation behaviors in high strength Al alloys by four-point bend fatigue testing under stress control. In this method, fatigue crack initiation sites (fatigue weak-links, FWLs) were measured on the sample surface at different cyclic stress levels. The FWL density in an alloy could be best described using a three-parameter Weibull function of stress, though other types of sigmoidal functions might also be used to quantify the relationship between FWL density and stress. The strength distribution of the FWLs was derived from the Weibull function determined by fitting the FWLs vs. stress curve experimentally obtained. As materials properties, the FWL density and strength distribution could be used to evaluate the fatigue crack nucleation behaviors of engineering alloys quantitatively and the alloy quality in terms of FWL density and strength distribution. In this work, the effects of environment, types of microstructural heterogeneities and loading direction on FWLs were all studied in detail in AA7075-T651, AA2026-T3511, and A713 Al alloys, etc. It was also found that FWLs should be quantified as a Weibull-type function of strain instead of stress, when the applied maximum cyclic stress exceeded the yield strength of the tested alloys. In this work, four-point bend fatigue tests were conducted on the L-T (Rolling-Transverse), L-S (Rolling-Short transverse) and T-S planes of an AA7075-T651 alloy plate, respectively, at room temperature, 20 Hz, R=0.1, in air. The FWL populations, measured on these surfaces, were a Weibull-type function of the applied maximum cyclic stress, from which FWL density and strength distribution could be determined. The alloy showed a significant anisotropy of FWLs with the weak-link density being 11 mm-2, 15 mm-2 and 4 mm-2 on the L-T, L-S and T-S planes, respectively. Fatigue cracks were predominantly initiated at Fe-containing particles on the L-T and L-S planes, but only at Si-bearing particles on the T-S plane, profoundly demonstrating that the pre-fractured Fe-containing particles were responsible for crack initiation on the L-T and L-S planes, since the pre-fracture of these particles due to extensive deformation in the L direction during the prior rolling operation could only promote crack initiation when the sample was cyclically stressed in the L direction on both the L-T and L-S planes. The fatigue strengths of the L-T, L-S and T-S planes of the AA7075 alloy were measured to be 243.6, 273.0 and 280.6 MPa, respectively. The differences in grain and particle structures between these planes were responsible for the anisotropy of fatigue strength and FWLs on these planes. Three types of fatigue cracks from particles, type-I: the micro-cracks in the particles could not propagate into the matrix, i.e., type-II: the micro-cracks were fully arrested soon after they propagated into the matrix, and type-III: the micro-cracks became long cracks, were observed in the AA7075-T651 alloy after fatigue testing. By cross-sectioning these three-types of particles using Focused Ion Beam (FIB), it was found that the thickness of the particles was the dominant factor controlling fatigue crack initiation at the particles, namely, the thicker a pre-fractured Fe-containing particle, the easier it became a type-III crack on the L-T and L-S planes. On the T-S plane, there were only types-I and III Si-bearing particles at which crack were initiated. The type-I particles were less than 6.5 μm in thickness and type-III particles were thicker than 8.3 μm. Cross-sectioning of these particles using FIB revealed that these particles all contained gas pores which promoted crack initiation at the particles because of higher stress concentration at the pores in connection with the particles. It was also found that fatigue cracks did not always follow the any specific crystallographic planes within each grain, based on the Electron Backscatter Diffraction (EBSD) measurement. Also, the grain orientation did not show a strong influence on crack initiation at particles which were located within the grains. The topography measurements with an Atomic Force Microscope (AFM) revealed that Fe-containing particles were protruded on the mechanically polished surface, while the Si-bearing particles were intruded on the surface, which was consistent with hardness measurements showing that Si-bearing particles were softer (4.030.92 GPa) than Fe-containing ones (8.9 0.87 GPa) in the alloy. To verify the 3-D effects of the pre-fractured particles on fatigue crack initiation in high strength Al alloys, rectangular micro-notches of three different types of dimensions were fabricated using FIB in the selected grains on the T-S planes of both AA2024-T351 and AA7075-T651 Al alloys, to mimic the three types of pre-fractured particles found in these alloys. Fatigue testing on these samples with the micro-notches verified that the wider and deeper the micro-notches, the easier fatigue cracks could be initiated at the notches. In the AA2024-T351 samples, cracks preferred to propagate along the {111} slip plane with the smallest twist angle and relatively large Schmid factor. These experimental data obtained in this work could pave a way to building a 3-D quantitative model for quantification of fatigue crack initiation behaviors by taking into account the driving force and resistance to short crack growth at the particles in the surface of these alloys.

The most promising applications for targeted alpha-therapy with astatine-211 (At-211) include treatments of disseminated microscopic disease, the major medical problem for cancer treatment. The primary advantages of targeted alpha-therapy with At-211 are that the alpha-particle radiation is densely ionizing, translating to high relative biological effectiveness (RBE), and short-range, minimizing damage to surrounding healthy tissues. In addition, theranostic imaging with I-123 surrogates has shown promise for developing new therapies with At-211 and translating them to the clinic. Currently, Canada does not have a way of producing At-211 by conventional methods because it lacks alpha-particle accelerators with necessary beam energy and intensity. The work presented here was aimed at studying the Rn-211/At-211 generator system as an alternative production strategy by leveraging TRIUMF's ability to produce rare isotopes. Recognizing that TRIUMF provided production opportunities for a variety of astatine isotopes, this work also originally hypothesized and evaluated the use of At-209 as a novel isotope for preclinical Single Photon Emission Computed Tomography (SPECT) with applications to At-211 therapy research. At TRIUMF's Isotope Separator and Accelerator (ISAC) facility, mass separated ion beams of short­-lived francium isotopes were implanted into NaCl targets where Rn-211 or At-209 were produced by radioactive decay, in situ. This effort required methodological developments for safely relocating the implanted radioactivity to the radiochemistry laboratory for recovery in solution. For multiple production runs, Rn-211 was quantitatively transferred from solid NaCl to solution (dodecane) from which At-211 was efficiently extracted and evaluated for clinical applicability. This validated the use of dodecane for capturing Rn-211 as an elegant approach to storing and shipping Rn-211/At-211 in the future. Po-207 contamination (also produced by Rn-211 decay) was removed using a granular tellurium (Te) column before proceeding with biomolecule labelling. Although the produced quantities were small, the pure At-211 samples demonstrated these efforts to have a clear path of translation to animal studies. For the first time in history, SPECT/CT was evaluated for measuring At-209 radioactivity distributions using high energy collimation. The spectrum detected for At-209 by the SPECT camera presented several photopeaks (energy windows) for reconstruction. The 77-90 Po X­-ray photopeak reconstructions were found to provide the best images overall, in terms of resolution/contrast and uniformity. Collectively, these experiments helped establish guidelines for determining the optimal injected radioactivity, depending on scan parameters. Moreover, At-209-based SPECT demonstrated potential for pursuing image-­based dosimetry in mouse tumour models, in the future. Simultaneous SPECT imaging with At-209 and I-123 was demonstrated to be feasible, supporting the future evaluation of At-209 for studying/validating I-123 surrogates for clinical image-based At-211 dosimetry. This work also pursued a novel strategy for labelling cancer targeting peptides with At-211, using octreotate (TATE, a somatostatin analogue for targeting tumour cells, mostly neuroendocrine tumours) prepared with or without N-terminus PEGylation (PEG2), followed by conjugation with a closo-decaborate linking moiety (B10) for attaching At-211. Binding affinity and in vivo biodistributions for the modified peptides were determined using iodine surrogates. The results indicated that B10-PEG2-TATE retained target binding affinity but that the labelling reaction with iodine degraded this binding affinity significantly, and although having high in vivo stability, no I-123-B10-PEG2-TATE tumour uptake was observed by SPECT in a mouse tumour model positive for the somatostatin receptor (sstr2a). This suggested that further improvements are required for labelling. A new method for producing At-211 at TRIUMF is established, and At-209-­based SPECT imaging is now demonstrated as a new preclinical technology to measure astatine biodistributions in vivo for developing new radiopharmaceuticals with At-211. Combined with the theranostic peptide labelling efforts with iodine, these efforts provide a foundation for future endeavours with At-211-­based alpha-therapy at TRIUMF. All procedures were performed safely and rapidly, suitable for preclinical evaluations. All animal studies received institutional ethics approval from the University of British Columbia (UBC). / Graduate

Les faisceaux d’électrons et d’ions sont au cœur de nombreuses techniques instrumentales servant à explorer, analyser et agir sur des matériaux à l’échelle du micromètre au nanomètre (Microscopie électronique, spectrométrie d’électrons, techniques de « FIB »). Les limites de résolution spatiale et énergétique de ces techniques dépendent en grande partie des propriétés des sources qu’elles utilisent et en particulier de leur température de fonctionnement. De fait, depuis plus de 10 ans, le potentiel des atomes froids ionisés comme nouveau type de source d’électrons ou d’ions est intensivement exploré.Le projet expérimental réalisé au LAC et décrit dans cette thèse utilise un jet d’atomes de césium issu d’un piège magnéto-optique à deux dimensions. La température transverse du jet est de l’ordre de 100 µK. Malgré cela, le jet est encore trop divergent après la sortie de la zone de refroidissement pour notre expérience. Afin guider le jet d’atomes jusqu’à la zone d’ionisation, nous avons étudié une méthode particulière de guidage dipolaire. L’utilisation d’un seul laser convenablement réglé nous a permis de guider et pousser les atomes du jet en même temps tout en limitant le chauffage. Nous avons ainsi pu compresser avec ce laser pousseur-guideur le jet d’atomes sur un diamètre de 400 µm à 60 cm de la zone de refroidissement du PMO-2D.Le jet est ensuite ionisé par la méthode d’ionisation en champ électrique statique d’atomes de Rydberg. Les atomes sont tout d’abord excités par laser sur un état de Rydberg (n~30) en présence d’un champ électrique uniforme et homogène. Les atomes du jet ainsi excités voyagent vers une zone présentant un fort gradient de champ où ils vont alors s’ioniser autour de la même valeur de potentiel, réduisant ainsi la taille de la zone d’ionisation et donc de la dispersion en énergie potentielle initiale du faisceau d’électron. La probabilité d’ionisation des atomes dans le champ dépend grandement de l’état de Rydberg préalablement excité. Le choix de l’état de Rydberg optimal, i.e. qui a une probabilité d’ionisation la plus grande possible, nécessite une étude de l’ionisation des états de Rydberg du césium. Un modèle à deux niveaux est présenté dans cette thèse qui permet de retrouver le comportement d’ionisation d’état de Rydberg observé expérimentalement. Ce modèle simple nous a permis de comprendre quel type d’état nous devions exciter. Enfin une étude expérimentale est également présentée. / Electron and Ion beams are at the base of many instrumental techniques used to explore, to analyse and to modify materials from the micrometer to the manometer scale (Electronic Microscopy, Electron Spectrometry, Focused Ion beams techniques…). Spatial and Energetic resolutions of these techniques are strongly dependent on its source‘s properties and particularly their working temperature. In fact, for more than ten years, the potential of ionised cold atoms have been intensively studied. Our experiment at LAC, described in this thesis, uses a 2 dimensional magneto-optical trap (2D-MOT) to create a caesium atomic beam. The transverse temperature of the beam is around 100 µK. Despite this, the beam is still too divergent after exiting the cooling area. To guide the atomic beam up to the ionisation area, we have studied and implemented a particular method of dipolar guiding. The use of a unique laser properly set allowed us to push and guide altogether the atoms of the beam while limiting the heating effect. Thus, we have managed to compress the atomic beam’s size to 400 µm at 60 cm from the output of the MOT.Afterward, the atomic beam is ionised by the method of Rydberg (static) field ionisation. The atoms are firstly excited by laser on a Rydberg state (n~30) as a static homogeneous and uniform electric field is applied. The excited atoms of beam travel therefore to a high-gradient field area where they ionise around the same electric potential value, therefore reducing the ionisation area’s size and the initial potential energy spread of the electron beam. The ionisation probability of the atoms in the field depends greatly on the excited Rydberg state. The choice of an optimal Rydberg state , i.e. with the highest probability of ionisation, needs better knowledge of the ionisation of cesium Rydberg states. A two levels model us to describe the ionisation behaviour of some Ryberg. This simple models helps to understand what kind of states we want to excite in order to optimise the ionisation area‘s size. An experimental study of cesium Rydberg states is also presented.

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.

Nos dias atuais, grande parte das intervenções cirúrgicas inclui o implante de materiais. Os grandes obstáculos na implantação de próteses em organismos humanos são a coagulação sanguínea em contato com o material devido ao alto grau de ativação plaquetária e a compatibilidade dos tecidos biológicos ao material implantado. Agregando melhorias de propriedades mecânicas a superfícies biocompatíveis, materiais poliméricos apresentam grandes tendências a serem excelentes candidatos a biomateriais para tais aplicações. O objetivo deste trabalho foi realizar modificações superficiais em polímeros através do método de implantação por feixe iônico a fim de se investigar mudanças induzidas em suas propriedades superficiais e estudar possíveis mudanças em sua biocompatibilidade, em específico, sua hemocompatibilidade. Amostras de policarbonato foram irradiadas com feixes de íons de argônio com energia 23 keV e cinco diferentes doses. As superfícies das amostras foram analisadas com medidas de ângulo de contato, microscopia de força atômica, espectroscopia de massa de íons secundários, espectroscopia de fotoelétrons, espectroscopia de retroespalhamento Rutherford, deteção de recuo elástico, espectroscopia de raios-X induzidos por partículas e testes de adesão plaquetária. Os resultados das diferentes técnicas apontaram de forma consistente a uma série de alterações químicas e físicas induzidas nas superfícies das amostras, dentre elas: a perda significativa de hidrogênio nas amostras irradiadas, aumento do grau de reticulação entre as cadeias poliméricas que levou ao aumento de elétron deslocalizados e mudança de coloração, remoção de aditivos, migração à superfície de átomos de argônio implantados e alteração de hidrofilicidade. Ao confrontar todos os resultados obtidos com os resultados dos testes de adesão plaquetária, constatou-se que os efeitos observados aumentam o caráter trombogênico da superfície do policarbonato e que a remoção de aditivos com grupos sulfato e sulfonato após irradiação com argônio teve grande influência em tal aumento. / In the current days, a big part of the surgical interventions includes the implant of materials. The great obstacles for prosthesis implantation in living organisms are the blood clotting when in contact to the material due to a high level of platelet activation and the biological tissues compatibility to the implanted material. By joining improvements on mechanical properties to biocompatible surfaces, polymer materials present high tendencies to be excellent biomaterials candidates for such applications. The objective of this work was to perform surface modification in polymers through the ion beam implantation method in order to investigate changes induced in their surface properties and study possible biocompatibility changes. Samples of polycarbonate were irradiated with argon ion beam with 23 keV energy and different doses. The surfaces of the samples were analyzed by contact angle measurements, atomic force microscopy, secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, elastic recoil detection, particle induced x-ray spectroscopy and platelet adhesion tests. The results from the different techniques pointed consistently to a series of chemical and physical changes induced on the samples\' surfaces, such as: significant loss of hydrogen for the irradiated samples, increase of cross-linking between polymer chains which led to the increase of delocalized electrons and color change, removal of additives, migration of argon atoms to the surface and hydrophilicity changes. By comparing all the obtained results to the platelet adhesion tests results, it was found that the observed effects increase the thrombogenic characteristic of the polycarbonate surface and that the removal of additives with sulfate and sulfonate groups after the argon irradiation had great influence on such increase.

Nos dias atuais, grande parte das intervenções cirúrgicas inclui o implante de materiais. Os grandes obstáculos na implantação de próteses em organismos humanos são a coagulação sanguínea em contato com o material devido ao alto grau de ativação plaquetária e a compatibilidade dos tecidos biológicos ao material implantado. Agregando melhorias de propriedades mecânicas a superfícies biocompatíveis, materiais poliméricos apresentam grandes tendências a serem excelentes candidatos a biomateriais para tais aplicações. O objetivo deste trabalho foi realizar modificações superficiais em polímeros através do método de implantação por feixe iônico a fim de se investigar mudanças induzidas em suas propriedades superficiais e estudar possíveis mudanças em sua biocompatibilidade, em específico, sua hemocompatibilidade. Amostras de policarbonato foram irradiadas com feixes de íons de argônio com energia 23 keV e cinco diferentes doses. As superfícies das amostras foram analisadas com medidas de ângulo de contato, microscopia de força atômica, espectroscopia de massa de íons secundários, espectroscopia de fotoelétrons, espectroscopia de retroespalhamento Rutherford, deteção de recuo elástico, espectroscopia de raios-X induzidos por partículas e testes de adesão plaquetária. Os resultados das diferentes técnicas apontaram de forma consistente a uma série de alterações químicas e físicas induzidas nas superfícies das amostras, dentre elas: a perda significativa de hidrogênio nas amostras irradiadas, aumento do grau de reticulação entre as cadeias poliméricas que levou ao aumento de elétron deslocalizados e mudança de coloração, remoção de aditivos, migração à superfície de átomos de argônio implantados e alteração de hidrofilicidade. Ao confrontar todos os resultados obtidos com os resultados dos testes de adesão plaquetária, constatou-se que os efeitos observados aumentam o caráter trombogênico da superfície do policarbonato e que a remoção de aditivos com grupos sulfato e sulfonato após irradiação com argônio teve grande influência em tal aumento. / In the current days, a big part of the surgical interventions includes the implant of materials. The great obstacles for prosthesis implantation in living organisms are the blood clotting when in contact to the material due to a high level of platelet activation and the biological tissues compatibility to the implanted material. By joining improvements on mechanical properties to biocompatible surfaces, polymer materials present high tendencies to be excellent biomaterials candidates for such applications. The objective of this work was to perform surface modification in polymers through the ion beam implantation method in order to investigate changes induced in their surface properties and study possible biocompatibility changes. Samples of polycarbonate were irradiated with argon ion beam with 23 keV energy and different doses. The surfaces of the samples were analyzed by contact angle measurements, atomic force microscopy, secondary ion mass spectroscopy, x-ray photoelectron spectroscopy, Rutherford backscattering spectroscopy, elastic recoil detection, particle induced x-ray spectroscopy and platelet adhesion tests. The results from the different techniques pointed consistently to a series of chemical and physical changes induced on the samples\' surfaces, such as: significant loss of hydrogen for the irradiated samples, increase of cross-linking between polymer chains which led to the increase of delocalized electrons and color change, removal of additives, migration of argon atoms to the surface and hydrophilicity changes. By comparing all the obtained results to the platelet adhesion tests results, it was found that the observed effects increase the thrombogenic characteristic of the polycarbonate surface and that the removal of additives with sulfate and sulfonate groups after the argon irradiation had great influence on such increase.

Este trabalho tem por objetivo a caracterização de filmes finos de óxido de alumínio produzidos por deposição assistida por feixe de íons Ar+. Tal caracterização consiste em estabelecer a relação entre os parâmetros de produção (energia do feixe e uxo relativo de Ar), a composição e a estrutura dos lmes. Para tanto, utiliza-se técnicas de microscopia de força atômica, difração de raios-x, reetividade de raios-x e análise por feixe iônico. Resultados mostram que amostras produzidas à temperatura ambiente e à 450 oC são amorfas independentemente da energia do feixe iônico. Filmes formados com assistência de feixe possuem qualidade superior àqueles formados por deposição física de vapor. O bombardeamento de íons Ar+ mostra-se capaz de controlar a concentração de hidrogênio, a estequiometria, a rugosidade, o tamanho dos grãos e a densidade dos lmes nos. Amostras com excelente qualidade baixa rugosidade, estequiometria próxima da ideal e boa densidade foram produzidas utilizando íons com energia dentre 300 eV e 600 eV. / The scope of this work is the characterization of aluminum oxide thin films produced by Ar+ ion beam assisted deposition. This characterization consists in establishing the relationship between production parameters (ion beam energy and argon relative ux), structure and composition of these lms. In order to undertake this task, the following techniques were used: atomic force microscopy, x-ray diraction, x-ray reectivity and ion beam analysis. Results show that samples produced at room temperature and at 450 oC are amorphous regardless the ion beam energy. Films grown under ion assistance have better characteristics than the ones deposited by physical vapor deposition. The ion beam bombardment is capable of controlling hydrogen concentration, stoichiometry, roughness, grain size and density of alumina samples. High quality lms at surface and increased density lms with near ideal stoichiometry were produced with 300 eV and 600 eV ion beam energy.

O carbeto de silício (SiC) é um semicondutor com propriedades adequadas para substituir o silício em dispositivos eletrônicos em aplicações que exijam alta potência, alta frequência e/ou alta temperatura. Além disso, é possível crescer termicamente um filme de dióxido de silício (SiO2) sobre o SiC de maneira análoga ao silício. Porém, esses filmes apresentam maior densidade de defeitos eletricamente ativos na região interfacial SiO2/SiC que no caso do SiO2/Si, o que limita a qualidade dos dispositivos formados. Assim, compreender a origem da degradação elétrica e desenvolver métodos para passivar os defeitos na região interfacial SiO2/SiC são importantes passos para o desenvolvimento da tecnologia do SiC. Buscando uma melhor compreensão da natureza dos defeitos presentes na região interfacial SiO2/SiC, a interação de estruturas SiO2/SiC com vapor d’água enriquecido isotopicamente (D2 18O) e a interação com monóxido de carbono (CO), um dos subprodutos da oxidação térmica do SiC, foram investigadas. Observou-se que a interação com CO gera cargas positivas na estrutura e que a incorporação de deutério proveniente da água é fortemente dependente da rota de formação do filme de SiO2. Sabendo que a incorporação de nitrogênio e de fósforo na região interfacial SiO2/SiC são eficientes métodos para reduzir o número de defeitos eletricamente ativos nessa região, investigou-se a incorporação de nitrogênio em estruturas de SiC através de tratamentos térmicos em amônia enriquecida isotopicamente (15NH3) e desenvolveu-se um novo método de incorporação de fósforo, fazendo sua deposição por pulverização catódica (sputtering) Os métodos de incorporação propostos resultaram em maiores quantidades de nitrogênio e de fósforo na região interfacial SiO2/SiC do que os encontrados na literatura, tornando-os promissores candidatos na passivação elétrica do SiC. Além da caracterização físico-química utilizando diferentes técnicas, também foi feita a caracterização elétrica de capacitores Metal-Óxido-Semicondutor (MOS) testando filmes de SiO2 obtidos por sputtering ou por crescimento térmico. Adicionalmente, desenvolveu-se uma rota de síntese de padrões de 18O mais estáveis ao longo do tempo para serem utilizados em análises por reação nuclear. Também foi proposta uma metodologia de quantificação de fósforo via análise por reação nuclear. Dos resultados obtidos neste doutorado, uma melhor compreensão da natureza e da origem dos defeitos presentes na região interfacial SiO2/SiC foi alcançada. Também obteve-se uma melhor compreensão de como os elementos passivadores nitrogênio e fósforo interagem nessa região. / Silicon carbide (SiC) is a semiconductor with adequate properties to substitute silicon in electronic devices in applications that require high power, high frequency, and/or high temperature. Besides, a silicon dioxide (SiO2) film can be thermally grown on SiC in a similar way to that on Si. However, these films present higher density of electrical defects in the SiO2/SiC interfacial region when compared to the SiO2/Si interface, which limits the quality of the fabricated devices. Thus, it is important to understand the origin of the electrical degradation and to develop methods to passivate the defects in the SiO2/SiC interfacial region in order to develop the SiC technology. Aiming at a better understanding of the nature of defects at the SiO2/SiC interfacial region, the interaction of SiO2/SiC structures with water vapor isotopically enriched (D2 18O) and the interaction with carbon monoxide (CO), one of the SiC thermal oxidation by-products, were investigated. It was observed that the interaction with CO generates positive charges in the structure and that the deuterium incorporation from the water vapor is strongly dependent on the formation route of the SiO2 film. Knowing that nitrogen and phosphorous incorporation in the SiO2/SiC interfacial region are efficient methods to reduce the number of electrical defects in this region, the nitrogen incorporation in SiC structures by isotopically enriched ammonia (15NH3) annealings was investigated and a new method to incorporate phosphorous, by sputtering deposition was developed The proposed incorporation methods resulted in higher amounts of nitrogen and phosphorous then those found in literature, making them promising candidates to the electrical passivation of SiC. Besides the physico-chemical characterization using different techniques, the electrical characterization of Metal-Oxide-Semiconductor (MOS) capacitors was also performed, testing SiO2 films obtained by sputtering deposition or thermally grown. Additionally, a route to synthesize 18O standards for nuclear reaction analyses that are more stable over time was developed. Besides, a methodology to quantify phosphorous by nuclear reaction analysis was proposed. From the results obtained in this PhD thesis, a better understanding of the nature and the origin of defects present in the SiO2/SiC interfacial region was obtained, as well as a better understanding on how the passivating elements nitrogen and phosphorous interact in this region.

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.