Defective structures in two-dimensional (2D) materials have been proved to have significant influences on the materials' properties. Understanding structural defects in 2D materials at atomic scale is therefore required. With the use of advanced imaging techniques, one of the main approaches applied in this project was aberration-corrected transmission electron microscopy (AC-TEM), the structures are able to be resolved with single-atom sensitivity with the reduction of both spherical aberration and the influence of chromatic aberration. This laid the foundation for the first two experiments, which involve the bond length measurement of each C-C bond within three types of divacancies and Si-C bonds at graphene edges. The former explains the tendency of bond rotations within the divacancies from the perspective of strain inside the defective areas and surrounding lattice; the latter revels the interactions between isolated Si atoms and zigzag/armchair graphene edges. The use of in-situ heating holder in the AC-TEM makes the direct visualization of structures and their dynamics at elevated temperatures possible. The Si-graphene edge interactions, as well as the following two experiments are all designed to study the high-temperature performances for different systems. Gold nanoclusters are introduced to monolayer graphene by thermal evaporation to study the interaction between gold and graphene at elevated temperature. Due to the strong interaction between gold and graphene, gold crystals are able to adapt to planar configurations with two different crystalline forms, and an epitaxial relationship was found for planar gold crystals and graphene. Atomically flat and long line defects and zigzag edges in monolayer molybdenum disulfide (MoS₂) are successfully created by in-situ thermal annealing. The relationship between S vacancy mobility and defect forms are revealed based on the experiment. High-temperature atomic configurations of line defects and edge terminations are resolved in the first time. Their electronic properties are also explored with the support of density functional theory calculations.

Amblyopia is the leading cause of monocular visual impairment in children. Therapy for amblyopia is extremely beneficial in some children but ineffective in others. It is critical that the reasons for this discrepancy are understood. Emerging evidence indicates that current clinical protocols for the diagnosis of amblyopia may not be sufficiently sensitive in identifying individuals who, on more detailed examination, exhibit subtle structural defects of the eye. Presently, the magnitude of this problem is unknown. The aim of this study was to establish the prevalence of subtle retinal/optic nerve head defects in eyes diagnosed with amblyopia, to distinguish between possible explanations for the origin of such defects and to investigate the relationship between quantitative measures of retinal structure, retinal nerve fibre layer thickness and optic nerve head dimensions. Using the imaging technique of Optical Coherence Tomography (OCT) retinal structure has been investigated in detail, following the visual pathway across the retina from the fovea, via the paramacular bundle to the optic disc, where peripapillary retinal nerve fibre thickness has been imaged and subjected to detailed measures along with optic disc size and shape. The study formed two phases, the first imaging the eyes of visually normal adults and children, comparing them to amblyopes, both adults and children who had completed their treatment. The second phase, a longitudinal study, investigated retinal structure of amblyopic children undertaking occlusion therapy for the first time. By relating pre-therapy quantitative measures to the visual outcome the second phase of the study aimed to examine whether OCT imaging could identify children achieving a poor final outcome. The results show a clear picture of inter-ocular symmetry structure in all individuals, visually normal and amblyopic. Optic disc characteristics revealed no structural abnormalities in amblyopes, in any of the measured parameters, nor was there any association between the level of visual acuity and the measured structure. At the fovea differences were shown to occur in the presence of amblyopia, with thickening of the fovea and reduction of the foveal pit depth. The structural changes were found to be both bilateral and symmetrical with the fellow eye also affected. In the longitudinal phase of the study these changes were demonstrated to a greater extent in children who 'failed' to respond to treatment. This bilateral, symmetrical structural change found at the fovea, which has not been previously reported, cannot therefore be the primary cause of the visual loss which has been diagnosed as amblyopia.

O composto magnético geometricamente frustrado Gd2Ti2O7 da família dos pirocloros apresenta um comportamento bastante interessante, sendo que a natureza da fase magnética em baixas temperaturas se encontra ainda sob intenso debate. Este material entra em um estado antiferromagnético parcialmente ordenado à temperatura T1N ~ 1 K, apresentando outra transição de fase em T2N ~ 0.7 K. Neste trabalho é investigada a física de baixas temperaturas de amostras de Gd2Ti2O7 com defeitos estruturais tais como vacâncias de oxigênio e diluição de ítrio. Amostras policristalinas com composição Gd2Ti2O7 e Gd2-xYxTi2O7 foram sintetizadas em diferentes condições por uma rota alternativa conhecida como método sol-gel. O refinamento de um modelo para os dados de difração de raios X mostra que vacâncias de oxigênio são os principais defeitos estruturais neste material. As vacâncias de oxigênio resultam numa ligeira diminuição de T1N e numa redução da magnetização de saturação. A diluição da rede com ítrio leva a uma clara diminuição de T1N e da temperatura de Curie-Weiss. Medidas de calor específico evidenciaram as duas transições T1N e T2N no composto com menor grau de vacâncias de oxigênio. A análise da contribuição magnética ao calor específico Cm em baixas temperaturas, 0.39 K < T < 0.68 K, revelou um comportamento proporcional a T^2 previamente discutido na literatura. Entretanto, verificamos que uma dependência T^3, usualmente encontrada em antiferromagnetos convencionais, descreve igualmente bem nossos dados experimentais resultando em uma velocidade de magnons consistente com a apresentada por outros pirocloros. / The geometrically frustrated compound Gd2Ti2O7 of the pyrochlore family displays such an interesting behaviour that the nature of the ordered magnetic phase at low temperatures is still under intense discussion. This material enters in a partially ordered magnetic state at a temperature T1N ~ 1 K, and there is another phase transition at T2N ~ 0.7 K. In this thesis we study the low temperature physics of Gd2Ti2O7 with structural defects such as oxygen vacancies and yttrium dilution. Polycrystalline samples of Gd2Ti2O7 and Gd2-xYxTi2O7 were synthesized in different conditions by an alternative route known as the sol-gel method. The refinement of a model for the X-ray diffraction data reveal that the oxygen vacancies are the leading defects in this material. The oxygen vacancies result in a slight decrease of T1N and in a reduction of the saturation magnetization. The yttrium dilution of the lattice leads to a clear reduction of T1N and of the Curie-Weiss temperature. Specific heat measurements display both transitions T1N and T2N in the compound with lower degree of oxygen vacancies. The analysis of the magnetic contribution to the specific heat Cm at low temperatures, 0.39 K < T < 0.68 K, reveals a behaviour proportional to T^2 previously discussed in the literature. However, we verify that a dependence T^3, usually found in standard antiferromagnets, describes similarly well our experimental data resulting in a velocity of magnons consistent with the ones exhibited for another pyrochlores.

Utilizando a técnica de ataque químico e microdureza realizamos um estudo sistemático dos defeitos estruturais e da microplasticidade em monocristais pertencentes ao sistema (BSCC) e em monocristais de LiNbO3. Desenvolvemos uma solução apropriada com HNO3 e H2O nas proporções de 1ml:30ml durante 20 segundos para o ataque químico dos compostos do sistema BSCC e revelamos padrões de defeitos estruturais como deslocações, terráceos (terraceds) e agrupamentos (bunchs). Além disso, fizemos uma tentativa de identificar a composição real destes compostos usando as técnicas de microscopia ótica, difração de raio-x, Laue, fluorescência de raio-x, medidas de resistividade, microdureza e ataque químico. O comportamento plástico/frágil dos cristais de Niobato de Lítio foi estudado nos planos (00.1), (01.4) e (01.0). Analisamos também a distribuição das deslocações em torno das deformações plásticas produzidas por indentações de uma ponta Vickers nas superfícies de pólos de domínios positivo e negativo sobre plano (00.1). Alguns desses resultados, como no caso da revelação de defeitos estruturais e microdureza dos compostos do sistema BSCC, podem ser considerados inéditos. Os cristais de niobato de lítio crescidos em nossos laboratórios mostraram um comportamento frágil isotrópico não convencional para esse composto, quando submetidos a tratamentos térmicos / We used etching and microindentation techniques to study the structural defects, microplasticity and microhardness in Bi-Sr-Ca-Cu-O and LiNbO3 single crystals. To revel structural defects in Bi-Sr-Ca-Cu-O crystals was developed a suitable solution of HNO3 in the ratio 1:30. The results obtained showed that there are patterns of structural defects as dislocations, terraceds and bunches in these compounds. We also did an attempt to identify the actual compositions of these compounds using optical microscopy, x-ray diffraction, Laue pattern, X-ray fluorescence, resistivity, microhardness and etching techniques. In LiNbO3 single crystals we analyzed the dislocations distributions around the plastic deformations produced by indentation experiments. The behavior plastic/fragile in LiNbO3 crystals were studied on three different perpendicular directions: to the Z-axis, to the 128 and to the (01.0). Some of these results, as the structural defects revelation and the microhardness in Bi-Sr-Ca-Cu-O compounds as well, were obtained at the first time. Also, unusual fragile behavior isotropic of LiNbO3 grown in our laboratory was found

O composto magnético geometricamente frustrado Gd2Ti2O7 da família dos pirocloros apresenta um comportamento bastante interessante, sendo que a natureza da fase magnética em baixas temperaturas se encontra ainda sob intenso debate. Este material entra em um estado antiferromagnético parcialmente ordenado à temperatura T1N ~ 1 K, apresentando outra transição de fase em T2N ~ 0.7 K. Neste trabalho é investigada a física de baixas temperaturas de amostras de Gd2Ti2O7 com defeitos estruturais tais como vacâncias de oxigênio e diluição de ítrio. Amostras policristalinas com composição Gd2Ti2O7 e Gd2-xYxTi2O7 foram sintetizadas em diferentes condições por uma rota alternativa conhecida como método sol-gel. O refinamento de um modelo para os dados de difração de raios X mostra que vacâncias de oxigênio são os principais defeitos estruturais neste material. As vacâncias de oxigênio resultam numa ligeira diminuição de T1N e numa redução da magnetização de saturação. A diluição da rede com ítrio leva a uma clara diminuição de T1N e da temperatura de Curie-Weiss. Medidas de calor específico evidenciaram as duas transições T1N e T2N no composto com menor grau de vacâncias de oxigênio. A análise da contribuição magnética ao calor específico Cm em baixas temperaturas, 0.39 K < T < 0.68 K, revelou um comportamento proporcional a T^2 previamente discutido na literatura. Entretanto, verificamos que uma dependência T^3, usualmente encontrada em antiferromagnetos convencionais, descreve igualmente bem nossos dados experimentais resultando em uma velocidade de magnons consistente com a apresentada por outros pirocloros. / The geometrically frustrated compound Gd2Ti2O7 of the pyrochlore family displays such an interesting behaviour that the nature of the ordered magnetic phase at low temperatures is still under intense discussion. This material enters in a partially ordered magnetic state at a temperature T1N ~ 1 K, and there is another phase transition at T2N ~ 0.7 K. In this thesis we study the low temperature physics of Gd2Ti2O7 with structural defects such as oxygen vacancies and yttrium dilution. Polycrystalline samples of Gd2Ti2O7 and Gd2-xYxTi2O7 were synthesized in different conditions by an alternative route known as the sol-gel method. The refinement of a model for the X-ray diffraction data reveal that the oxygen vacancies are the leading defects in this material. The oxygen vacancies result in a slight decrease of T1N and in a reduction of the saturation magnetization. The yttrium dilution of the lattice leads to a clear reduction of T1N and of the Curie-Weiss temperature. Specific heat measurements display both transitions T1N and T2N in the compound with lower degree of oxygen vacancies. The analysis of the magnetic contribution to the specific heat Cm at low temperatures, 0.39 K < T < 0.68 K, reveals a behaviour proportional to T^2 previously discussed in the literature. However, we verify that a dependence T^3, usually found in standard antiferromagnets, describes similarly well our experimental data resulting in a velocity of magnons consistent with the ones exhibited for another pyrochlores.

Cette thèse a pour but de discuter les mécanismes à l’origine de la for-mation, de l’activité pour la réduction de l’oxygène (ORR) et de la sta-bilité de nanoparticules (NPs) creuses à base de Pt supportées sur car-bone pour des applications en pile à combustible à membrane échan-geuse de protons (PEMFC). La formation et la croissance des NPs, syn-thétisées par une méthode dite ‘one-pot’, ont été étudiées par l’inter-médiaire de mesures microscopiques, électroniques et de diffraction, nous permettant ainsi de mettre en évidence les différentes étapes de la synthèse. Le procédé de synthèse a été étendu à différents métaux non nobles (M = Ni, Co, Cu, Zn and Fe) et à différents supports carbonés. L’activité supérieure des NPs pour l’ORR résulte (i) de la contraction du paramètre de maille induit par la présence du métal non-noble, (ii) de leur porosité ouverte et (iii) de la densité de défauts structuraux à la surface des NPs (rationalisée via COads stripping et analyse de Riet-veld). Les défauts structuraux se seront montrés plus stables que le mé-tal non-noble durant les tests de vieillissement accéléré. / This thesis investigates the mechanisms driving the formation, the en-hanced activity for the oxygen reduction reaction (ORR) and the dura-bility of porous hollow PtM/C nanoparticles (NPs) for proton exchange membrane fuel cell (PEMFC) applications. The formation and growth of the NPs, synthesized by a ‘one-pot’ process, were discussed in the light of microscopic, in operando X-ray and electronic measurements, unveiling the different intermediate steps of the synthesis. The synthe-sis process was extended to different non-noble metals (M = Ni, Co, Cu, Zn and Fe) and to different carbon supports. The enhanced activity for the ORR resulted from (i) the contraction of the lattice parameter by the non-noble metal (the final NPs contains ca. 15 – 20 at. % of M), (ii) the open porosity and (iii) the density of structural defects at the surface of the NPs, rationalized by COads stripping measurments and Rietveld analysis. The non-noble metal was found to segregate faster than the structural defects during the accelerated stress tests.

Utilizando a técnica de ataque químico e microdureza realizamos um estudo sistemático dos defeitos estruturais e da microplasticidade em monocristais pertencentes ao sistema (BSCC) e em monocristais de LiNbO3. Desenvolvemos uma solução apropriada com HNO3 e H2O nas proporções de 1ml:30ml durante 20 segundos para o ataque químico dos compostos do sistema BSCC e revelamos padrões de defeitos estruturais como deslocações, terráceos (terraceds) e agrupamentos (bunchs). Além disso, fizemos uma tentativa de identificar a composição real destes compostos usando as técnicas de microscopia ótica, difração de raio-x, Laue, fluorescência de raio-x, medidas de resistividade, microdureza e ataque químico. O comportamento plástico/frágil dos cristais de Niobato de Lítio foi estudado nos planos (00.1), (01.4) e (01.0). Analisamos também a distribuição das deslocações em torno das deformações plásticas produzidas por indentações de uma ponta Vickers nas superfícies de pólos de domínios positivo e negativo sobre plano (00.1). Alguns desses resultados, como no caso da revelação de defeitos estruturais e microdureza dos compostos do sistema BSCC, podem ser considerados inéditos. Os cristais de niobato de lítio crescidos em nossos laboratórios mostraram um comportamento frágil isotrópico não convencional para esse composto, quando submetidos a tratamentos térmicos / We used etching and microindentation techniques to study the structural defects, microplasticity and microhardness in Bi-Sr-Ca-Cu-O and LiNbO3 single crystals. To revel structural defects in Bi-Sr-Ca-Cu-O crystals was developed a suitable solution of HNO3 in the ratio 1:30. The results obtained showed that there are patterns of structural defects as dislocations, terraceds and bunches in these compounds. We also did an attempt to identify the actual compositions of these compounds using optical microscopy, x-ray diffraction, Laue pattern, X-ray fluorescence, resistivity, microhardness and etching techniques. In LiNbO3 single crystals we analyzed the dislocations distributions around the plastic deformations produced by indentation experiments. The behavior plastic/fragile in LiNbO3 crystals were studied on three different perpendicular directions: to the Z-axis, to the 128 and to the (01.0). Some of these results, as the structural defects revelation and the microhardness in Bi-Sr-Ca-Cu-O compounds as well, were obtained at the first time. Also, unusual fragile behavior isotropic of LiNbO3 grown in our laboratory was found

Amblyopia is the leading cause of monocular visual impairment in children. Therapy for amblyopia is extremely beneficial in some children but ineffective in others. It is critical that the reasons for this discrepancy are understood. Emerging evidence indicates that current clinical protocols for the diagnosis of amblyopia may not be sufficiently sensitive in identifying individuals who, on more detailed examination, exhibit subtle structural defects of the eye. Presently, the magnitude of this problem is unknown. The aim of this study was to establish the prevalence of subtle retinal/optic nerve head defects in eyes diagnosed with amblyopia, to distinguish between possible explanations for the origin of such defects and to investigate the relationship between quantitative measures of retinal structure, retinal nerve fibre layer thickness and optic nerve head dimensions. Using the imaging technique of Optical Coherence Tomography (OCT) retinal structure has been investigated in detail, following the visual pathway across the retina from the fovea, via the paramacular bundle to the optic disc, where peripapillary retinal nerve fibre thickness has been imaged and subjected to detailed measures along with optic disc size and shape. The study formed two phases, the first imaging the eyes of visually normal adults and children, comparing them to amblyopes, both adults and children who had completed their treatment. The second phase, a longitudinal study, investigated retinal structure of amblyopic children undertaking occlusion therapy for the first time. By relating pre-therapy quantitative measures to the visual outcome the second phase of the study aimed to examine whether OCT imaging could identify children achieving a poor final outcome. The results show a clear picture of inter-ocular symmetry structure in all individuals, visually normal and amblyopic. Optic disc characteristics revealed no structural abnormalities in amblyopes, in any of the measured parameters, nor was there any association between the level of visual acuity and the measured structure. At the fovea differences were shown to occur in the presence of amblyopia, with thickening of the fovea and reduction of the foveal pit depth. The structural changes were found to be both bilateral and symmetrical with the fellow eye also affected. In the longitudinal phase of the study these changes were demonstrated to a greater extent in children who ¿failed¿ to respond to treatment. This bilateral, symmetrical structural change found at the fovea, which has not been previously reported, cannot therefore be the primary cause of the visual loss which has been diagnosed as amblyopia.

<p>Research in the area of improving the efficiency and manufacturability of alternative energy technologies has been of high interest due to the growing environmental concerns of energy resources. Group III-antimonide-based compound semiconductors have been sought after as excellent candidates for photovoltaic conversion of infrared radiation, outside the spectral range absorbed by the currently available crystalline Si solar cells. The major challenge is the GaSb/Si interface is highly lattice mismatched, and inherently heterovalent. This leads to a high density of structural defects, many of which have not been investigated fully. Both optical and electrical properties of such heteroepitaxy thin films are strongly dependent on the periodicity of the crystal lattice, and the presence of extended defects cause perturbations in the lattice periodicity. Therefore the nature of such extended defects must be understood, in order to better manipulate the growth process to minimize their presence. This thesis demonstrates that through the use of conventional transmission electron microscopy, further insight can be gained into understanding the origin, distribution, propagation, and interaction of various extended defects. From this, a couple of ways to systematically suppress some of the defects have also been implemented, and the mechanism by which they induce such a suppression is also discussed.</p> / Master of Applied Science (MASc)

A aplicação de Ensaios Não Destrutivos (END) é considerada uma alternativa para monitorar o estado das estruturas de concreto armado, principalmente quando ocorrem falhas de projeto, erros de dosagem, problemas na mistura, transporte ou lançamento do concreto. A medida da Velocidade de Pulso Ultrassônico (VPU) é um END que vem sendo usado comumente em diversas áreas da engenharia civil, devido à facilidade da operação, ao seu baixo custo, à rapidez na execução dos testes e à ausência de danos ao material analisado. O objetivo deste trabalho consiste em apresentar o resultado de uma pesquisa experimental, que visou estudar a influência que determinadas variáveis operacionais exercem sobre os resultados obtidos nos ensaios de VPU e qual a real capacidade de penetração e detecção de defeitos de diversas magnitudes. As medições foram realizadas utilizando o ultrassom pelo modo de transmissão indireta, pois esta é a alternativa que mais se adapta às condições verificadas no exame de estruturas reais de concreto armado. Primeiramente, foram moldados em laboratório dois blocos de concreto, com dimensões próximas às encontradas em estruturas reais de grande porte: um com armadura nas duas faces e outro sem armadura. Em ambos os elementos foram introduzidos objetos para simular possíveis falhas de concretagem. Em uma segunda etapa, foram realizadas perfurações visando identificar a capacidade de detecção de vazios da técnica de VPU para diferentes profundidades. Os resultados são apresentados na forma de imagens geradas através de software e por meio de analises estatísticas. Este estudo verificou que a escolha dos parâmetros de ensaio é um fator determinante para permitir a interpretação correta dos resultados, salientando-se que a experiência do operador e as dimensões de grid são os parâmetros que mais interferem na interpretação dos dados. / The use of Non-destructive Testing (NDT) methods is considered an alternative to monitor the behaviour of reinforced concrete structures, especially when there are design problems or errors related to concrete mixing, transport, placement and casting errors. The Ultrasonic Pulse Velocity (UPV) method is a Non-Destructive Test that is gaining acceptance. The test has been commonly used in various civil engineering areas due to the fact that it is easy to operate and rapid to perform, and to the low cost and lack of damage to the tested material. The objective of this work is to present the results of an experimental research that aimed to study the influence of certain technological variables on the measurements obtained from UPV tests. The work also aims to gather data to assess the penetration capacity of the US waves and their ability to detect defects of various dimensions. The measurements were performed using the indirect transmission mode, to simulate real work conditions on large structures. Firstly, two massive concrete blocks were cast in the laboratory, with dimensions close to real life structures: one with steel reinforcement on both sides and the other without reinforcement. Objects were introduced in both elements to simulate possible defects due to casting. In a second stage, perforations were conducted in the concrete elements to identify the void detection capability of the UPV technique for different depths. The results are presented by images generated by specific software and by using statistical analysis. This study found that the test parameters influence significantly the correct interpretation of the results. The operator experience and the grid dimensions are the parameters that most influence UPV data analysis.