Simulation of crack growth in the internal cooling system of a blade in a Siemens gas turbine has been studied by inserting and propagating cracks at appropriate locations. The softwares used are ABAQUS and FRANC3D, where the latter supports finite element meshing of a crack and calculation of the stress intensities along the crack front based on the results from an external finite element program. The blade is subjected to thermo-mechanical fatigue and the cracks are grown subjected to in-phase loading conditions.   The material of the blade is STAL15SX, a nickel-base single-crystal superalloy. The <001> crystalline direction is aligned with the loading direction of the blade, while the secondary crystalline directions are varied to examine how it affects the thermo-mechanical crack propagation fatigue life of the blade.   The finite element model is set up using a submodeling technique to reduce the computational time for the simulations. Investigations to validate the submodeling technique are conducted.   From the work it can be concluded that a crack located at a critical location in the cooling lattice reach above the crack propagation target life. Cracks located at noncritical locations have crack propagation lives of a factor 5.2 times the life of the critical crack.

Experimental micromechanics of materials is a branch of science that seeks to build tight connections between composition, structure, processing and performance of materials under specific operating conditions required for particular technology applications. The present project is focused on the development of techniques that use the combination of electron, ion and X-ray microscopies to study the deformation behaviour of a particularly important class of metallic alloys used in the manufacture of aeroengines, namely, the so-called Ni-base superalloys. The complex hierarchical structure of these materials means that their macroscopic response is controlled to a great extent by the phenomena that play out on very fine scales, from angstroms (lattice spacing dimension) to nanometres (precipitates, phase boundaries, dislocations, chemical inhomogeneities) to microns (grains and their boundaries, defects and their clusters, dislocation pileups) to millimetres (component scale). Understanding the fine structure and deformation behaviour requires the development of specially configured experimental setup that allow the observation and quantification of deformation to external loading. In this study, FIB-SEM methods for sample characterization and fabrication were combined with synchrotron-based X-ray diffraction and imaging techniques, and backed up by theoretical analysis and numerical simulation, to elucidate the origins of the strength of these alloys. Micropillar compression tests using in-SEM nanoindentation were used to reveal the size dependence of the apparent strength, and connection was made with the dislocation-mediated crystal slip to provide an explanation of the observed Hall-Petch type dependence with a modified Hall-Petch equation considering both intrinsic and extrinsic characteristic lengths introduced. X-ray scattering was used in the polychromatic micro-Laue mode and using Bragg coherent diffractive imaging to reveal the crystal distortion arising due to plastic deformation. A Discrete dislocation dynamics in the 2.5D formulation was used to obtain a model description of the observed phenomena. The key outcome of the work presented in this thesis lies in the successful development of advanced observational tools and relevant theoretical or computational models for mesoscale plasticity problems for crystal with complex microstructure.

This thesis project has focused on the development of high-pressure single-crystal diffraction experiments on the neutron Laue diffractometer KOALA at the OPAL reactor at ANSTO, Australia. Over the course of this project several candidate systems have been studied under conditions of high-pressure using X-ray diffraction with a view to their use in developmental experiments on KOALA. The results of two high-pressure KOALA experiments are presented as well as the notable results from X-ray diffraction on the candidate systems. The first experiment on hexamethylenetetramine provided valuable insights into how reduced crystallite size and reciprocal-space access affects data collected on KOALA. In addition, data treatment techniques were developed to deal with the unique and challenging high-pressure Laue data, including corrections for attenuation due to the cell body. The ability to collect data through the body of cell prompted a further experiment on the complex, low-symmetry structure of the amino acid l-arginine dihydrate. Despite the smaller crystal size and dominant parasitic scattering from the diamond-anvil cell, the data collected allow a full anisotropic refinement of hexamethylenetetramine with bond lengths and angles that agree with literature data within experimental error. This technique is highly suited to low-symmetry crystals, as shown by the successful refinement of data from a l-arginine dihydrate crystal. In such cases the transmission of diffracted beams results in higher completeness values than are possible with X-rays. The hydrogen-bonded ferroelectric rubidium hydrogensulfate was the subject of ambient-pressure experiments on KOALA investigating the nature of the ferroelectric transition. Further high-pressure X-ray diffraction studies were carried out to resolve the structures of phases at high-pressure and to investigate the ferroelectric transition under pressure. The potassium cobalt citrate metal-organic framework UTSA-16 has shown a wide variety of pressure-mediated framework-solvent interactions including negative linear compressibility, the ordering of potassium ions, and coordination changes which were investigated by high-pressure single-crystal and powder X-ray diffraction. These behaviors are rationalised by examination of the structural changes occurring in the framework under pressure. Two members of the widely studied alkylammonium tetrachlorometallate family, tetramethylammonium tetrachloroferrate(III) and tetramethylammonium tetrachlorogallate(III), display numerous phase transitions with temperature. The structures of these phases have been determined for the first time, and the contrast between the two materials explored with first-principles calculations.

O presente trabalho mostra um estudo sobre a presença de pares de íons de CN- - Cu+ e OCN- -Cu+, em cristais de KCl, usando técnicas de medidas de corrente de despolarização termoestimulada (I.T.C.) e Absorção óptica. A detecção destes pares foi feita através de um estudo sistemática de correlação entre as diferentes amostras aqui usadas: KCl + 1% KCN; KCl + 1% CuCl; KCl + 1% KOCN; KCl + 1% KOCN + 1% CuCl e KCl + 1% KCN + 1% CuCl. Deve ser ressaltado que a última amostra apresenta um tipo de impureza não intencional OCN- , cuja associação com o íon Cu+ também é observada. Na absorção ótica observamos bandas à temperatura ambiente em 210, 228, 242, 252, 260 e 290 nm para o cristal de KCl + 1% CuCl + 1% KCN, sendo que para o cristal de KCl + 1% KOCN + 1% CuCl não foi observado o último pico. As diferentes bandas são atribuídas às possíveis interações entre Cu+ e CN-, bem como Cu+ e OCN-. Quanto à técnica de ITC, as curvas obtidas por esta, para os três últimos cirstais citados acima, foram melhor ajustadas pela somatória de duas curvas singulares de ITC, cujas temperaturas de pico estão nas posições de 53 e 55 K; 54,3 e 56,6 K; 53,3 e 56,1 K, respectivamente. Em KCl + 1% KOCN a curva de mais baixa temperatura (curva 1) de ITC é atribuída à molécula (16O12C14N-) e a curva de mais alta temperatura (curva 2) é atribuída à molécula isotrópica (18O12C14N-). Para as amostras de KCl + 1% KOCN + 1% CuCl a curva 1 foi atribuída ao OCN- isolado e a curva 2 ao Cu+ perturbado pela presença do OCN-. Quanto ao cristal de KCl + 1% KCN + 1% CuCl, as duas técnicas propostas não foram suficientes para identificar a presença de pares Cu+ - CN-, necessitando, desta maneira, da utilização de outra técnica experimental, como por exemplo a da luminescência. A correlação dos resultados experimentais foi feita através dos parâmetros determinados do momento de dipolo (p), energia de ativação (Ea&#8727) e a temperatura de pico (Tm&#8727) / The present work gives a study on CN- - Cu+ and OCN- -Cu+ coupled pairs doped KCl single crystal, by using Ionic Thermal Current (I.T.C.) and Optical absorption techniques. These pairs were detected through a systematic correlation study between different samples: KCl + 1% KCN; KCl + 1% CuCl; KCl + 1% KOCN; KCl + 1% KOCN + 1% CuCl and KCl + 1% KCN + 1% CuCl, were the last sample shows unporposely doping OCN-, compled with Cu+. The observed optical absorption bands, at room temperature, were in 210, 228, 242, 252, 260 and 290 nm for KCl + 1% CuCl + 1% KCN crystal. Only the last absorption band was not seen in KCl + 1% KOCN + 1% CuCl samples. Diferent bands are associated with possible interactions between Cu+ and CN-, as also Cu+ with OCN-. The ITC curves for the last three crystals were better fitted with two single ITC´s curves, whose temperature peaks are at 53 and 55 K; 54,3 and 56,6 K; 53,3 and 56,1 K, respectively. The lowest temperature ITC band (curve 1) in KCl + 1% KOCN is attributed to the (16O12C14N-) molecule and the highest temperature ITC band (curve 2) is due to the (18O12C14N-) isotropic molecule. For KCl + 1% KOCN + 1% CuCl samples curve 1 was associated with isolated OCN- and curve 2 with Cu+ perturbed with OCN-. With KCl + 1% KCN + 1% CuCl, the two techniques were not good enough to identify Cu+ - CN-, compling, it should be necessary to apply another type of techniques, like luminescence. The correlations of the experimental results were done through the determination electric dipole moment (p), activation energy (Ea&#8727) and temperature peak (Tm&#8727) parameters

Realizamos crescimento de monocristal de Hexafluoreto de Fósforo e Potássio:KPF6 pelo método de crescimento em solução aquosa e o estudo das propriedades elétricas. Para isso foram feitas medidas, de solubilidade, tempo de incubação, espectroscopia dispersiva no infra-vermelho, difração de raios-X, condutividade elétrica e constante dielétrica no intervalo de temperatura de hélio líquido a 300&#176C. Foram detectadas três transições de fases estruturais em APROXIMADAMENTE 0&#176C, -14,4&#176C e 193&#176C e impurezas de CO-23, responsável pelo aumento da condutividade elétrica na região extrínsica. Na defermação do grupo PF6 durante a transição de fase estrutural em -14,4&#176C há surgimento de um dipolo elétrico com valor de 12,2x10-18ues.cm. E observamos o congelamento do grupo PF6 por volta de -41&#C / It was made the growth of a Potassium Hexafluophosphate: KPF6 monocrystal method of growth in aqueous solution and the study of its electrical properties. With this purpose, it was use of solubility, incubation time, dispersive espectroscopy on the infrared region, X-ray diffraction, electrical conductivity and dieletrical Constant in the range of temperature between liquid helium and 573K. It was detected three strutural phase transitions in 273K, 258,6K and 80K and impurities like CO-23. In the deformation of the PF6 group, during the structural phase transition in 258,6K, electrical dipole appears with a value 12,2.10-18ues.cm. It was observed the freezing of PF6 group near 232K

Submitted by Franciele Moreira (francielemoreyra@gmail.com) on 2017-11-08T14:07:09Z No. of bitstreams: 2 Dissertação - Ana karolline Silva Mendanha Valdo - 2017.pdf: 18131682 bytes, checksum: 99cf3e17fe7f0bb93c35ab0c28a8f865 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-11-09T10:02:22Z (GMT) No. of bitstreams: 2 Dissertação - Ana karolline Silva Mendanha Valdo - 2017.pdf: 18131682 bytes, checksum: 99cf3e17fe7f0bb93c35ab0c28a8f865 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-11-09T10:02:22Z (GMT). No. of bitstreams: 2 Dissertação - Ana karolline Silva Mendanha Valdo - 2017.pdf: 18131682 bytes, checksum: 99cf3e17fe7f0bb93c35ab0c28a8f865 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-10-10 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This work investigates the trending of crystallization in non-centrosymmetric space groups to study second harmonic generation (SGH) in the field of non linear optics. Using trans-1,2-di(4-pyridil)ethylene (BPE) four unpublished compounds were obtain, being them BPEH2Cl2·2H2O (1), BPEH2Br2 (2), BPEH2(H2PO4)2 (3) e BPEH2(H2PO4)2·H3PO4 (4). In these structures was possible to analyse the pattern of formed synthons, which showed to be function of geometry and polarizability and not only of acid strength of acid that generates the counter ion. The structure 1 showed pseudo symmetry and had the space group determined by the combination of observed signal of second harmonic generation and statistical parameters of refinement in different space groups. Under the incidence of LASER with emission on 974 nm it was observed a signal dependent of the incident power in 487 nm for single crystals of these structure, proving the absence of inversion center in 1. All structures were characterized by single-crystal X-ray diffraction (SXRD), with additional caracterizations for structure 1 using the techniques X-ray powder diffraction (PXRD), photoluminescence, measurement of second harmonic generation signal and theorical calculation of SHG effects and eletrical properties. / Esse trabalho investiga a tendência de cristalizações em grupos espaciais não centrossimétricos para o estudo de geração de segundo harmônico (GSH) na área de óptica não linear. Utilizando a trans-1,2-di(4-piridil)etileno (BPE) quatro compostos inéditos foram obtidos, sendo eles BPEH2Cl2·2H2O (1), BPEH2Br2 (2), BPEH2(H2PO4)2 (3) e BPEH2(H2PO4)2·H3PO4 (4). Nessas estruturas foi possível analisar o padrão de síntons formados, que mostram ser dependentes da geometria e polarizabilidade e não só da força ácida do ácido que gera o contra-íon. A estrutura 1 apresentou pseudosimetria e teve o grupo espacial determinado pela combinação do sinal de geração de segundo harmônico e estatística do refinamento em diferentes grupos espaciais. Sob incidência do LASER em 974 nm foi observado um sinal dependente da potência em 487 nm para os cristais dessa estrutura, comprovando a ausência do centro de simetria em 1. Todas as estruturas foram caracterizadas por difração de Raios X por monocristal (DRXM), com caracterizações adicionais para estrutura 1 pelas técnicas de difração de Raios X de pó (DRXP), fotoluminescência, obtenção do sinal de geração de segundo harmônico e cálculos teóricos dos efeitos de GSH e de propriedades elétricas.

Nos últimos 30 anos o crescimento paralelo das Ciências de Superfície tradicionais, em ambiente de ultra-alto vácuo (UHV), com a Eletroquímica levou ao nascimento de um novo campo interdisciplinar: Física de Superfície e Eletroquímica. Técnicas de ambas as áreas dão informações complementares e assim, quando realizadas em conjunto podem fornecer muitas respostas em nível atômico, estrutural e eletrônico quando o eletrodo está em contato com a solução eletrolítica. A intenção primordial dessa Dissertação foi o estudo fundamental das fases ricas em oxigênio presentes na superfície de Ru(0001) através de caracterizações eletroquímicas e morfológicas utilizando um sistema que permitiu o acoplamento de uma célula eletroquímica miniatura de fluxo a câmaras de UHV. Inicialmente exibi-se a modificação e a construção de equipamentos necessários para a preparação do sistema binário Au-Pt(111) e do óxido monocristalino Ru2O(110). Imagens de STM em escala morfológica mostraram o crescimento anisotrópico do filme de RuO2(110) sobre um substrato monocristalino de Ru(0001). Resultados obtidos através da técnica de Voltametria Cíclica na eletrooxidação de CO em RuO2(110) corroboraram cálculos teóricos sobre a estrutura da superfície quando esta em ambiente úmido. Superfícies modelos baseadas em ouro, crescido epitaxialmente sobre um substrato de Pt(111), foram preparadas no sistema de UHV. Dados eletroquímicos foram correlacionados às composições superficiais destas, mostrando o efeito do substrato prevalecendo sobre o efeito eletrônico. / In the last 30 years the parallel growth of the traditional Surface Science, under UHV environment, and Electrochemistry gave rise to a new interdisciplinary field: Surface Science and Electrochemistry. Techniques from both sciences give complementary information. Thus, in tandem, they are able to elucidate many atomic, structural and electronic phenomena, of an electrode in contact with a solution. The main goal of this Dissertation was the fundamental study of the Oxygen-rich Ru(0001) surface through electrochemical and morphologic characterizations using a coupled system which allowed the attachment of a miniature flow cell to UVH-chambers. Initially it is shown the construction and modifications of required equipments for the preparation of the binary system Au-Pt(111) and single crystal RuO2(110) oxide. Attainable morphological STM images demonstrated the anisotropic growth of the RuO2(110) over a Ru(0001) substrate. Results of the electrooxidation of CO on RuO2(110), obtained by means of Cyclic Voltammetry, corroborated theoretical calculations concerning the oxide superficial structure in a humid environment. Model surfaces based on Au, epitaxialy grown on a Pt(111) substrate, were prepared under UHV conditions. Electrochemical data and superficial composition were correlated, confirming that the substrate effect overcomes electronic strain effects.

Neste trabalho foi estudado o crescimento de fibras da matriz LiLa(WO4)2 (LLW) pura e co-dopada com íons Yb3+ e Er3+ via micro pulling-down. Foram crescidas fibras homogêneas e transparentes de LiLa(WO4)2:Yb3+:Er3+ com teor de dopante de 2, 5, 7, 10 e 15 mol% de Yb3+, todas co-dopadas com teor de 0,5 mol% de Er3+, com 1mm de diâmetro e até 22 mm de comprimento. Partindo-se da dopagem de 20 mol% não foi possível o crescimento de fibras com a mesma qualidade das demais, ocorrendo segregação e, possivelmente, formação de fase secundária. A temperatura de fusão dos compostos diminui com a adição de Yb3+, indo de 1020°C para o LLW puro, para 991°C com dopagem de 20 mol%. Para a análise de espectroscopia de emissão, as fibras foram excitadas com laser na região do infravermelho em 972 nm, sendo observada a emissão dos íons Er3+ via conversão ascendente. Foram observadas emissões referentes às transições 4S3/2 → 4I15/2 (centroide em 550 nm), 2H11/2 → 4I15/2 (527 nm) e 4F9/2 → 4I15/2 (653 nm); sendo a primeira a mais intensa. A eficiência de emissão aumentou de ~7% para a fibra pura, para 36% na fibra com 15 mol% de Yb3+. Foi encontrado que, para a maior intensidade de emissão, a quantidade ideal de Yb3+ deve ser de 11,5 mol%. / In the current work, was studied the growth of pure and Yb3+ and Er3+-doped LiLa(WO4)2 (LLW) by micro pulling-down technique. Were grown homogeneous and transparent fibers of Yb3+:Er3+:LiLa(WO4)2 with a dopant content of 2, 5, 7, 10 and 15 mol% of Yb3+, all co-doped with 0.5 mol% Er3+, 1 mm diameter and up to 22 mm length. It was not possible grow fibers with 20 mol% of Yb3+ due segregation and, possibly, formation of secondary phases. Noticed the melting temperature of the doped compounds decreases with the addition of Yb3+, from 1020 °C (pure LLW) to 991 °C (20 mol% Yb-doped). For emission studies, the fibers were excited in the infrared region at 972 nm and up conversion emission of Er3+ ions was registered. Emissions referring to transitions 4S3/2 → 4I15/2 (centroid at 550 nm), 2H11/2 → 4I15/2 (527 nm) and 4F9/2 → 4I15/2 (653 nm) were observed; the first one being the most intense. Emission efficiency increased from ~ 7% in pure fiber to 36% in doped fiber with 15 mol% of Yb3+. It was found that, for the highest emission intensity, the ideal amount of Yb3+ should be 11.5 mol%.

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

No presente trabalho foi estudado catalisadores dispersos em carbono contendo Pt, PtRh e PtRhRu para eletroxidação de etanol. Os catalisadores foram preparados em ultra-som e caracterizados por EDX, DRX e MET e sua atividade catalítica estudada através das técnicas de voltametria cíclica e DEMS. Os resultados experimentais indicaram que a adição de ródio diminui o potencial de início de oxidação de etanol, embora também diminua a corrente faradáica. Os estudos de DEMS mostraram que com a presença de ródio há um aumento na produção de CO2. Devido a isso, estudos fundamentais em monocristais de Pt (111), Pt (110) e Pt (100) modificados com depósitos de Rh foram realizados. Os depósitos foram feitos pelo método eletroquímico e diferentes graus de recobrimentos foram estudados para a eletroxidação de etanol. A atividade catalítica foi avaliada por voltametria cíclica, cronoamperometria e FTIR in situ. Os resultados mostraram que quanto maior a quantidade de ródio na superfície menor é a corrente obtida na oxidação de etanol. Dentre os eletrodos monocristalinos estudados a Pt (100) apresentou melhor atividade para a oxidação etanol. Os estudos com monocristais corroboraram com os resultados obtidos para os catalisadores dispersos em carbono. / In this work, carbon dispersed catalysts containing Pt, PtRh and PtRhRu were studied for electroxidation of ethanol. The catalysts were prepared using ultrasound and characterized by EDX, XRD and TEM and its catalytic activity studied using the techniques of cyclic voltammetry and DEMS. Experimental results indicated that the addition of rhodium decreases the potential onset of ethanol oxidation, but also decrease the faradaic current. DEMS studies showed that the presence of rhodium promotes an increase in CO2 production. Because of this, fundamental studies on single crystal of Pt (111), Pt (110) and Pt (100) modified with Rh deposits were done. The deposits were made by electrochemical method and different degrees of coatings were studied for ethanol electroxidation The catalytic activity was evaluated by cyclic voltammetry, chronoamperometry and in situ FTIR. The results showed that the greater the amount of rhodium on the surface the lower the current obtained in the oxidation of ethanol. Among the electrodes studied monocrystalline Pt (100) showed the best activity for ethanol oxidation.