A precise understanding of the fundamental correlation between synthesis, microstructure and physical properties is of vital importance towards rational design of improved functional epitaxial thin films. With the presence of heterogeneous interface and associated inhomogeneous lattice strain, film microstructure becomes sensitive to subtle interfacial perturbations and hence may exhibit intriguing physical properties. Control of the epitaxial film functionality requires accurate knowledge of the actual film chemistry, interfacial defects and associated strain field. This dissertation reports in-depth microstructural characterization of the intrinsic chemical inhomogeneity in selected epitaxial thin films including superconducting Fe1+yTe1-xSex/SrTiO3(STO) heterogeneous systems, the flux-pinning defects at both of conversional YBa2Cu3O7-δ (YBCO)/substrate lateral interfaces and vertical interfaces of YBCO&BaSnO3(BSO) nanocomposite films, and the misfit dislocation core configurations of STO/MgO and MgO/STO heterostructures pair, using the state-of-the-art aberration-corrected scanning transmission electron microscopy (CS-corrected STEM) in combination with geometric phase analysis (GPA). For the first time, the local atomic arrangement of Te and Se as well as interstitial Fe(2) has been clearly revealed in superconducting Fe1+yTe1-xSex/STO epitaxial films. We found that the film growth atmosphere can greatly affect the film stoichiometry, the homogeneity of Se/Te ordering and thus the overall film superconductivity. YBCO/substrate interface mismatch and YBCO&BSO vertical interface contact have been explored through substrate selection and doping-concentration variation. We observed a diverse nature of intrinsic defects in different YBCO/substrate heterosystems; thermal stable defects capable of maintaining individual strain field have been found effective in flux-pinning. Along the vertical heterointerface of YBCO/BSO, misfit dislocations were found throughout the film thickness. It adds another dimension to the flux-pinning landscape design. Four basic misfit dislocation core configurations of a STO/MgO heterosystem have been identified, and found strongly dependent on the actual interface disordering such as substrate atomic-height steps and interdiffussion. To precisely quantify the heterointerface lattice strain, we first conducted systematic investigations on the accuracy of STEM-based GPA. Follow our protocol, 1 pm accuracy has been proven in the STEM fast-scan direction with a spatial resolution less than 1 nm. The effectiveness and reliability of this optimized GPA strain profile were demonstrated in both applications of a relaxed STO/MgO and a partially strained LaAlO3/STO heterointerfaces, respectively.

<p>The present dissertation investigated the impact of scales / scoring methods and prompt linguistic features on the meausrement quality of L2 English elicited imitation (EI). Scales / scoring methods are an important feature for the validity and reliabilty of L2 EI test, but less is known (Yan et al., 2016). Prompt linguistic features are also known to influence EI test quaity, particularly item difficulty, but item discrimination or corpus-based, fine-grained meausres have rarely been incorporated into examining the contribution of prompt linguistic features. The current study addressed the research needs, using item response theory (IRT) and random forest modeling.</p><p>Data consisted of 9,348 oral responses to forty-eight items, including EI prompts, item scores, and rater comments, which were collected from 779 examinees of an L2 English EI test at Purdue Universtiy. First, the study explored the current and alternative EI scales / scoring methods that measure grammatical / semantic accuracy, focusing on optimal IRT-based measurement qualities (RQ1 through RQ4 in Phase Ⅰ). Next, the project identified important prompt linguistic features that predict EI item difficulty and discrimination across different scales / scoring methods and proficiency, using multi-level modeling and random forest regression (RQ5 and RQ6 in Phase Ⅱ).</p><p>The main findings were (although not limited to): 1) collapsing exact repetition and paraphrase categories led to more optimal measurement (i.e., adequacy of item parameter values, category functioning, and model / item / person fit) (RQ1); there were fewer misfitting persons with lower proficiency and higher frequency of unexpected responses in the extreme categories (RQ2); the inconsistency of qualitatively distinguishing semantic errors and the wide range of grammatical accuracy in the minor error category contributed to misfit (RQ3); a quantity-based, 4-category ordinal scale outperformed quality-based or binary scales (RQ4); sentence length significantly explained item difficulty only, with small variance explained (RQ5); Corpus-based lexical measures and phrase-level syntactic complexity were important to predicting item difficulty, particularly for the higher ability level. The findings made implications for EI scale / item development in human and automatic scoring settings and L2 English proficiency development.</p>

Nos casos de perda óssea vertical severa, principalmente em áreas posteriores da mandíbula, uma alternativa às cirurgias de enxerto ósseo, pouco empregada e estudada, é a utilização de prótese parcial fixa (PPF) com cantilever distal. Pensando no material de infraestrutura que garanta resistência adequada para suportar as forças mastigatórias em longo prazo, aliado ao desenvolvimento da zircônia (Zr) e da tecnologia CAD/CAM, o objetivo deste estudo foi avaliar o desajuste vertical, perda de torque, resistência à fratura do cantilever e distribuição de tensões em PPFs parafusadas sobre implantes do tipo cone morse, confeccionadas em diferentes materiais de infraestrutura (Co-Cr [Fundição Convencional] e Co-Cr e Zr [CAD/CAM]) e posicionadas na área correspondente à região posterior da mandíbula. Foram confeccionadas 40 PPFs com cantilever distal e distribuídas em 5 grupos (n=8), de acordo com o material da infraestrutura: 1 Co-Cr (Fundição convencional soldagem a laser); 2 Co-Cr (Fundição convencional soldagem TIG); 3 Co-Cr (Fundição convencional monobloco); 4 Co-Cr (CAD/CAM) e 5 Zr (CAD/CAM). A análise do desajuste vertical foi realizada em 4 momentos distintos, com auxílio de estereomicroscopia (aumento de 50×) e usando o método de Sheffiled: T0 Infraestrutura no modelo mestre; T1 Infraestrutura no modelo de poliuretano, antes da aplicação do revestimento cerâmico; T2 PPF após aplicação do revestimento cerâmico e antes da ciclagem termomecânica e T3 PPF após da ciclagem termomecânica. A avaliação do afrouxamento de parafusos foi realizada antes (T2) e após (T3) a ciclagem termomecânica e foi obtida com o auxílio de um torquímetro digital com precisão de 0,1 N.cm. Para a realização da ciclagem termomecânica as PPFs foram posicionadas na máquina de ensaio e uma carga de 120 N foi aplicada sobre elas, buscando simular 14 meses de utilização (1.200.000 ciclos). A resistência máxima à fratura do cantilever foi determinada por meio do ensaio de flexão e, para isso, uma carga perpendicular ao longo eixo da peça protética foi aplicada, com uma velocidade de aproximação de 0,5 mm/min. Uma nova PPF para cada grupo foi confeccionada para ser utilizada na avaliação da distribuição de tensões quando elas foram submetidas a carregamento puntiforme no cantilever e oclusal distribuído (150 N), por meio de análise fotoelástica. Em geral, PPFs com infraestruturas em monobloco (G3) apresentaram maiores desajustes verticais, especialmente no elemento solto da segunda e terceira condição experimental e foram associados com maior concentração de tensões, tanto no carregamento puntiforme (360,07 kPa) quanto oclusal distruído (302,46 kPa). Por outro lado, infraestruturas obtidas por meio do sistema CAD/CAM mostraram os menores desajustes verticais, se assemelhando estatisticamente (p>0,05), em vários momentos, com infraestruturas soldadas e melhores distribuições de tensões, atingindo valores inferiores a 280 kPa no carregamento puntiforme e a 200 kPa no oclusal distribuído. A moldagem de transferência (T0 &rarr; T1) e a ciclagem termomecânica (T2 &rarr; T3) pouco influenciaram no desajuste vertical dos grupos. Já o processo de aplicação do revestimento cerâmico (T1 &rarr; T2) e o seu efeito cumulativo com a ciclagem termomecânica (T1 &rarr; &rarr; T3) foram responsáveis por alterações consideráveis no desajuste vertical dos grupos, sobretudo naqueles fundidos convencionalmente (G1, G2 e G3). A ciclagem termomecânica teve um efeito considerável no percentual de perda de torque intragrupo (pMolar=0,039; pPré-molar=0,044), embora comparações entre os diferentes grupos não tenham demonstrado significância estatística (pMolar=0,116; pPré-molar=0,334). PPFs com infraestrutura metálica (>410,83±72,26 N) apresentaram resistência à fratura consideravelmente maior (p<0,05) do que a zirconia (277,47±39,10 N) e os primeiros sinais de fratura do revestimento cerâmico foram observados em torno de 900 N. Dentro das limitações deste estudo, PPFs com infraestruturas confeccionadas por meio do sistema CAD/CAM foram associadas com melhor adaptação cervical e distribuição de tensões, embora a secção das infraestruturas seguida de soldagem pode também ser uma alternativa viável, com base na proximidade dos valores de desajustes verticais e distribuição de tensão. Adicionalmente, PPFs com infraestruturas em zircônia podem ser usadas com certo grau de segurança, tendo em vista a boa adaptação marginal e distribuição de tensões, bem como altos valores de resistência à fratura constatados. / In cases of severe vertical bone loss, especially in posterior region of the mandible, an alternative to bone graft surgery, little used and studied, is the use of implant-supported cantilever fixed partial denture (FPD). Thinking about the framework material that ensures adequate strength to resist the masticatory loads in long term, together with the development of zirconia (Zr) and of CAD/CAM technology, the aim of this study is to evaluate the vertical misfit, torque loss and fracture resistance of cantilever and stress distribution in FPDs screwretained on Morse taper implants, fabricated with different framework materials (Co-Cr [Conventional Casting] and Co-Cr and Zr [CAD/CAM]) and positioned on the posterior region of the mandible. Forty FPDs with distal cantilever were fabricated and distributed into 5 groups (n=8), according to framework material: 1 Co-Cr (Conventional casting laser welding); 2 Co-Cr (Conventional casting TIG welding); 3 Co-Cr (Conventional casting one-piece); 4 Co-Cr (CAD/CAM) and 5 Zr (CAD/CAM). Analysis of vertical misfit was performed in 4 different moments, using stereomicroscopy (50× magnification) and the Sheffield method: T0 Framework on master model; T1 Framework on polyurethane model, before the ceramic veneering application; T2 FPD after application of the ceramic veneering and before the thermomechanical cycling and T3 FPD after thermomechanical cycling. Evaluation of screw loosening was performed before (T2) and after (T3) thermomechanical cycling and was obtained by a digital torque wrench with an accuracy of 0.1 N.cm. To perform the thermomechanical cycling, FPDs were positioned in the testing machine, and a 120 N load was applied on them, seeking to simulate 14 months of use (1,200,000 cycles). Fracture maximum resistance of the cantilever was determined by the flexural test and, therefore, a perpendicular force on the cantilever was applied at a crosshead speed of 0.5 mm/min. A new FDP for each group was fabricated to be used in the evaluation of the stress distribution, when they were submitted to punctiform on the cantilever and oclusal distributed loads (150 N), by the photoelastic analysis. In general, FPDs with one-piece frameworks (G3) presented higher vertical misfits, especially in the element not tightened of the second and third experimental conditions, and were associated with higher stress concentration in both the punctiform (360.07 kPa) and oclusal distributed (302.46 kPa) loads. On the other hand, the frameworks obtained by the CAD/CAM system showed the smaller vertical misfits, being statistically similar (p>0.05) to welded frameworks at various times, and better stress distributions, reaching values less than 280 kPa in the punctiform load and 200 kPa in the occlusal distributed load. Transfer impression (T0 &rarr; T1) and thermomechanical cycling (T2 &rarr; T3) had little effect on vertical misfit of the groups. The application process of the ceramic veneering (T1 &rarr; T2) and its cumulative effect with thermomechanical cycling (T1 &rarr;T3) were responsible for considerable changes in vertical misfit of the group, especially in those conventionally cast (G1, G2 and G3). A thermomechanical cycling had considerable effect in the percentage of intragroup torque loss (pMolar=0.039; pPré-molar=0.044), although comparisons between the different groups did not show statistical significance (pMolar=0.116; pPrémolar= 0.334). FPDs with metal frameworks (>410.83±72.26 N) showed considerably higher fracture resistance (p<0.05) than zirconia (277.47±39.10 N) and the first signs of fracture of the ceramic veneering were observed around 900 N. Within the limitations of this study, FPDs with frameworks fabricated using the CAD/CAM system were associated with better cervical adaptation and stress distribution, although the section of the frameworks followed by welding may also be a viable alternative, based on the proximity of the values of vertical misfits and stress distribution. Additionally, FPDs with zirconia frameworks can be used with some degree of security, considering the good marginal adaptation and stress distribution, as well as high values of fracture resistance verified.

Nos casos de perda óssea vertical severa, principalmente em áreas posteriores da mandíbula, uma alternativa às cirurgias de enxerto ósseo, pouco empregada e estudada, é a utilização de prótese parcial fixa (PPF) com cantilever distal. Pensando no material de infraestrutura que garanta resistência adequada para suportar as forças mastigatórias em longo prazo, aliado ao desenvolvimento da zircônia (Zr) e da tecnologia CAD/CAM, o objetivo deste estudo foi avaliar o desajuste vertical, perda de torque, resistência à fratura do cantilever e distribuição de tensões em PPFs parafusadas sobre implantes do tipo cone morse, confeccionadas em diferentes materiais de infraestrutura (Co-Cr [Fundição Convencional] e Co-Cr e Zr [CAD/CAM]) e posicionadas na área correspondente à região posterior da mandíbula. Foram confeccionadas 40 PPFs com cantilever distal e distribuídas em 5 grupos (n=8), de acordo com o material da infraestrutura: 1 Co-Cr (Fundição convencional soldagem a laser); 2 Co-Cr (Fundição convencional soldagem TIG); 3 Co-Cr (Fundição convencional monobloco); 4 Co-Cr (CAD/CAM) e 5 Zr (CAD/CAM). A análise do desajuste vertical foi realizada em 4 momentos distintos, com auxílio de estereomicroscopia (aumento de 50×) e usando o método de Sheffiled: T0 Infraestrutura no modelo mestre; T1 Infraestrutura no modelo de poliuretano, antes da aplicação do revestimento cerâmico; T2 PPF após aplicação do revestimento cerâmico e antes da ciclagem termomecânica e T3 PPF após da ciclagem termomecânica. A avaliação do afrouxamento de parafusos foi realizada antes (T2) e após (T3) a ciclagem termomecânica e foi obtida com o auxílio de um torquímetro digital com precisão de 0,1 N.cm. Para a realização da ciclagem termomecânica as PPFs foram posicionadas na máquina de ensaio e uma carga de 120 N foi aplicada sobre elas, buscando simular 14 meses de utilização (1.200.000 ciclos). A resistência máxima à fratura do cantilever foi determinada por meio do ensaio de flexão e, para isso, uma carga perpendicular ao longo eixo da peça protética foi aplicada, com uma velocidade de aproximação de 0,5 mm/min. Uma nova PPF para cada grupo foi confeccionada para ser utilizada na avaliação da distribuição de tensões quando elas foram submetidas a carregamento puntiforme no cantilever e oclusal distribuído (150 N), por meio de análise fotoelástica. Em geral, PPFs com infraestruturas em monobloco (G3) apresentaram maiores desajustes verticais, especialmente no elemento solto da segunda e terceira condição experimental e foram associados com maior concentração de tensões, tanto no carregamento puntiforme (360,07 kPa) quanto oclusal distruído (302,46 kPa). Por outro lado, infraestruturas obtidas por meio do sistema CAD/CAM mostraram os menores desajustes verticais, se assemelhando estatisticamente (p>0,05), em vários momentos, com infraestruturas soldadas e melhores distribuições de tensões, atingindo valores inferiores a 280 kPa no carregamento puntiforme e a 200 kPa no oclusal distribuído. A moldagem de transferência (T0 &rarr; T1) e a ciclagem termomecânica (T2 &rarr; T3) pouco influenciaram no desajuste vertical dos grupos. Já o processo de aplicação do revestimento cerâmico (T1 &rarr; T2) e o seu efeito cumulativo com a ciclagem termomecânica (T1 &rarr; &rarr; T3) foram responsáveis por alterações consideráveis no desajuste vertical dos grupos, sobretudo naqueles fundidos convencionalmente (G1, G2 e G3). A ciclagem termomecânica teve um efeito considerável no percentual de perda de torque intragrupo (pMolar=0,039; pPré-molar=0,044), embora comparações entre os diferentes grupos não tenham demonstrado significância estatística (pMolar=0,116; pPré-molar=0,334). PPFs com infraestrutura metálica (>410,83±72,26 N) apresentaram resistência à fratura consideravelmente maior (p<0,05) do que a zirconia (277,47±39,10 N) e os primeiros sinais de fratura do revestimento cerâmico foram observados em torno de 900 N. Dentro das limitações deste estudo, PPFs com infraestruturas confeccionadas por meio do sistema CAD/CAM foram associadas com melhor adaptação cervical e distribuição de tensões, embora a secção das infraestruturas seguida de soldagem pode também ser uma alternativa viável, com base na proximidade dos valores de desajustes verticais e distribuição de tensão. Adicionalmente, PPFs com infraestruturas em zircônia podem ser usadas com certo grau de segurança, tendo em vista a boa adaptação marginal e distribuição de tensões, bem como altos valores de resistência à fratura constatados. / In cases of severe vertical bone loss, especially in posterior region of the mandible, an alternative to bone graft surgery, little used and studied, is the use of implant-supported cantilever fixed partial denture (FPD). Thinking about the framework material that ensures adequate strength to resist the masticatory loads in long term, together with the development of zirconia (Zr) and of CAD/CAM technology, the aim of this study is to evaluate the vertical misfit, torque loss and fracture resistance of cantilever and stress distribution in FPDs screwretained on Morse taper implants, fabricated with different framework materials (Co-Cr [Conventional Casting] and Co-Cr and Zr [CAD/CAM]) and positioned on the posterior region of the mandible. Forty FPDs with distal cantilever were fabricated and distributed into 5 groups (n=8), according to framework material: 1 Co-Cr (Conventional casting laser welding); 2 Co-Cr (Conventional casting TIG welding); 3 Co-Cr (Conventional casting one-piece); 4 Co-Cr (CAD/CAM) and 5 Zr (CAD/CAM). Analysis of vertical misfit was performed in 4 different moments, using stereomicroscopy (50× magnification) and the Sheffield method: T0 Framework on master model; T1 Framework on polyurethane model, before the ceramic veneering application; T2 FPD after application of the ceramic veneering and before the thermomechanical cycling and T3 FPD after thermomechanical cycling. Evaluation of screw loosening was performed before (T2) and after (T3) thermomechanical cycling and was obtained by a digital torque wrench with an accuracy of 0.1 N.cm. To perform the thermomechanical cycling, FPDs were positioned in the testing machine, and a 120 N load was applied on them, seeking to simulate 14 months of use (1,200,000 cycles). Fracture maximum resistance of the cantilever was determined by the flexural test and, therefore, a perpendicular force on the cantilever was applied at a crosshead speed of 0.5 mm/min. A new FDP for each group was fabricated to be used in the evaluation of the stress distribution, when they were submitted to punctiform on the cantilever and oclusal distributed loads (150 N), by the photoelastic analysis. In general, FPDs with one-piece frameworks (G3) presented higher vertical misfits, especially in the element not tightened of the second and third experimental conditions, and were associated with higher stress concentration in both the punctiform (360.07 kPa) and oclusal distributed (302.46 kPa) loads. On the other hand, the frameworks obtained by the CAD/CAM system showed the smaller vertical misfits, being statistically similar (p>0.05) to welded frameworks at various times, and better stress distributions, reaching values less than 280 kPa in the punctiform load and 200 kPa in the occlusal distributed load. Transfer impression (T0 &rarr; T1) and thermomechanical cycling (T2 &rarr; T3) had little effect on vertical misfit of the groups. The application process of the ceramic veneering (T1 &rarr; T2) and its cumulative effect with thermomechanical cycling (T1 &rarr;T3) were responsible for considerable changes in vertical misfit of the group, especially in those conventionally cast (G1, G2 and G3). A thermomechanical cycling had considerable effect in the percentage of intragroup torque loss (pMolar=0.039; pPré-molar=0.044), although comparisons between the different groups did not show statistical significance (pMolar=0.116; pPrémolar= 0.334). FPDs with metal frameworks (>410.83±72.26 N) showed considerably higher fracture resistance (p<0.05) than zirconia (277.47±39.10 N) and the first signs of fracture of the ceramic veneering were observed around 900 N. Within the limitations of this study, FPDs with frameworks fabricated using the CAD/CAM system were associated with better cervical adaptation and stress distribution, although the section of the frameworks followed by welding may also be a viable alternative, based on the proximity of the values of vertical misfits and stress distribution. Additionally, FPDs with zirconia frameworks can be used with some degree of security, considering the good marginal adaptation and stress distribution, as well as high values of fracture resistance verified.

Ce travail présente, dans trois systèmes différents, l'étude de nouveaux oxydes à structures incommensurables. Le composé $Ba_6Mn_{24}O_{48}$ ($Ba_{0.25}MnO_2$) possède une structure constituée par une charpente d'octaèdres $MnO_6$ dont l'arrangement définit des tunnels de type rutile, hollandite et des tunnels plus larges appelés "double barrelled". Les phénomènes d'incommensurabilité et de diffusion diffuse rencontrés dans ce composé sont décrits et expliqués par la distribution particulière des baryum dans les tunnels hollandite et "double barrelled". L'existence d'oxydes à structures lamellaires désaccordées est démontrée avec les composés de formulation $A'_{\alpha}[(AO)_{\frac{1+x}{2}}]_n(CoO_2)$. Ils sont construits sur la succession, selon un axe d'empilement, de (n-1) couches [AO] de type $NaCl$ et d'une couche hexagonale d'octaèdres $CoO_6$ joints par les arêtes. La transition entre ces deux couches est assurée par un élément de post-transition A'. Des termes n=2, avec $A'=Tl$ ou $Hg/Pb$ et des termes n=3 avec $A'=Bi$ ont été isolés. Dans les deux cas, le cation $A$ est $Sr$ et/ou $Ca$. Les composés ($Ba_{2-3x}Bi_{3x-}$)($Fe_{2x}Bi_{1-2x}$)$O_{3-\delta}$ ($x\in$[1/3, 1/2]), dérivés de la pérovskite, présentent des structures modulées de symétrie quadratique pour $x>0.4$. En utilisant le formalisme des groupes de superespace, une étude par analyse Rietveld montre que c'est la c\oe xistence sur le m\^{e}me site A pérovskite des cations $Ba$ et $Bi$ qui est responsable du phénomène d'incommensurablité observé. La structure magnétique de ces composés, déterminée par diffraction neutronique, est de type antiferromagnétique avec ferromagnétisme faible.

Conditioning geologic models to production data and assessment of uncertainty is generally done in a Bayesian framework. The current Bayesian approach suffers from three major limitations that make it impractical for field-scale applications. These are: first, the CPU time scaling behavior of the Bayesian inverse problem using the modified Gauss-Newton algorithm with full covariance as regularization behaves quadratically with increasing model size; second, the sensitivity calculation using finite difference as the forward model depends upon the number of model parameters or the number of data points; and third, the high CPU time and memory required for covariance matrix calculation. Different attempts were used to alleviate the third limitation by using analytically-derived stencil, but these are limited to the exponential models only. We propose a fast and robust adaptation of the Bayesian formulation for inverse modeling that overcomes many of the current limitations. First, we use a commercial finite difference simulator, ECLIPSE, as a forward model, which is general and can account for complex physical behavior that dominates most field applications. Second, the production data misfit is represented by a single generalized travel time misfit per well, thus effectively reducing the number of data points into one per well and ensuring the matching of the entire production history. Third, we use both the adjoint method and streamline-based sensitivity method for sensitivity calculations. The adjoint method depends on the number of wells integrated, and generally is of an order of magnitude less than the number of data points or the model parameters. The streamline method is more efficient and faster as it requires only one simulation run per iteration regardless of the number of model parameters or the data points. Fourth, for solving the inverse problem, we utilize an iterative sparse matrix solver, LSQR, along with an approximation of the square root of the inverse of the covariance calculated using a numerically-derived stencil, which is broadly applicable to a wide class of covariance models. Our proposed approach is computationally efficient and, more importantly, the CPU time scales linearly with respect to model size. This makes automatic history matching and uncertainty assessment using a Bayesian framework more feasible for large-scale applications. We demonstrate the power and utility of our approach using synthetic cases and a field example. The field example is from Goldsmith San Andres Unit in West Texas, where we matched 20 years of production history and generated multiple realizations using the Randomized Maximum Likelihood method for uncertainty assessment. Both the adjoint method and the streamline-based sensitivity method are used to illustrate the broad applicability of our approach.

xxiv, 265 p. : ill. (some col.) / Stabilizing mechanisms and design considerations for generating misfit layer compounds with a variety of different structural motifs were explored using designed precursors consisting of elemental layers. Layer order in the precursor film and the behavior of binary reaction couples was used to avoid undesirable reaction intermediates. Electron diffraction patterns of CuCr2 Se4 were inconsistent with prior reports that this compound has the spinel structure and were more consistent with a hexagonal R 3 ̄ structure. STEM imaging also suggests CuCr2 Se4 prepared using the compositionally modulated kinetic trapping approach is a new polymorph of the spinel structure. Electrical and magnetic properties were consistent with prior literature reports. Magnetic susceptibility measurements show pronounced hard and easy axes of magnetization not previously documented, which are consistent with a hexagonal crystal symmetry. The [{(PbSe)m }0.99 (WSe2 )n ] r and [{(PbSe)m }1.00 (MoSe2 )n ] r systems were investigated by STEM, XRD and density functional theory (DFT) modeling. No crystallographic registration between MSe and TSe 2 layers was observed and the diffraction observed in the hk 0 and hkl directions, where h = k = 0, can be described by diffraction from discrete layers of finite thickness. A distortion of the MX structure for m > 4 was documented. The distortion in MSe layers was largest for m = 2 and independent of TSe2 thickness. A novel family of compounds, [{(FeSe)m }1+y (NbSe 2 )n ]r , were synthesized inspired by a geological precedent. Single FeSe and NbSe2 layer thicknesses ((0.571 ± 0.005) nm and (0.653 ± 0.002) nm respectively) are consistent with literature values for the binary compounds. STEM-HAADF images of the [{(FeSe) 5 }1+y (NbSe2 )5 ]r revealed a multilayer structure with two distinct structural subunits. STEM-EELS analysis of the film showed no intermixing between the Nb and Fe regions within the limit of the measurement. Another family of misfit layer compounds, [{(NbSe2 )m }1+y (CuCr2Se4)n]r, designed to test requirements for a stable misfit layer compound, were successfully synthesized. STEM analysis of the [{(NbSe2 )5 }1+y (CuCr2 Se4 ) 1 ]r compound showed a well segregated film with two distinct subunit structures. Thicknesses for individual layers of NbSe2 or CuCr2 Se4 ((0.648 ± 0.004) nm and (1.76 ± 0.01) nm respectively) are consistent with prior literature reports of the individual binary compounds. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Dr. Mark C. Lonergan, Chair; Dr. David C. Johnson, Advisor; Dr. James Hutchison, Member; Dr. Catherine Page, Member; Dr. Stephen Gregory, Outside Member; Dr. Ian M. Anderson, Honorary Member

Made available in DSpace on 2014-07-29T15:21:57Z (GMT). No. of bitstreams: 1 pre textuais richard esteves pereira.pdf: 111431 bytes, checksum: fed09c5e1bc065f1fe26c77537645e5e (MD5) Previous issue date: 2005-03-24 / The adaptation precision of metallic structures to implant abutments is a very questionable subject and the scientific literature lacks about the alloy that shows an adaptation closer to the ideal. This study had the proposal of: evaluating the vertical marginal misfit levels (in &#956;m) using a digital microscope of one-piece and after laser welding metallic structures of total fixed implant supported prosthesis casted in Nickel-Chrome, Nickel-Chrome-Titanium-Molibidenium and Palladium-Silver alloys and commercially pure Titanium, over two different kinds of abutments and, also, associate the misfit results observed at the one-piece structures phase with the data obtained after the laser welding treatment. After the fabrication of two master models, 40 pre-fabricated copings for both Estheticone and Micro-Unit type abutments were used at the survey. Eight metallic structures were casted with Ni-Cr, Ni-Cr-Ti-Mo, Pd-Ag and Ti-c.p., being two structures for each alloy. The vertical misfit values concerning the relation of the metallic structures and implant abutments from all alloys and on both stages one-piece and after laser welding were tabulated and then submitted to statistical tests. The values were exposed to the ANOVA and the significant statistic means were compared by the Tukey test considering a 5% significance value (p<0.05), as well as the standard deviation. The results evidenced that the one-piece structures showed misfit, but the mean values did not present statistic significant differences. The material (alloys) analysis showed that the Ti-c.p. did not show discrepant mean values, but the same did not occur with the other alloys. The comparison between all alloys showed no significant statistical differences, and, the Pd-Ag alloy (control group) showed the higher misfit mean values at the one-piece phase. The relation between the one-piece and after laser welding phases showed the presence of statistic significant values, based on the mean values (onepiece= 0.0953 &#956;m / laser welding=0.0452 &#956;m) and the marginal vertical misfit after laser welding appeared significantly decreased. / A precisão da adaptação das infra-estruturas sobre pilares de implantes é objeto de inúmeros questionamentos e a literatura ainda é carente em relação à liga que possa apresentar adaptação próxima do ideal. Assim, esta pesquisa teve como propósitos: avaliar os níveis de desajustes marginais verticais (em &#956;m) por meio de microscópio mensurador digital das infra-estruturas metálicas em monobloco e após soldagem a laser de próteses totais fixas fundidas em ligas de Níquel-Cromo, Níquel-Cromo-Titânio-Molibidênio, Paládio-Prata e Titânio Comercialmente Puro assentadas sobre dois tipos diferentes de pilares de implantes e, ainda, correlacionar os resultados obtidos dos níveis de desajustes das infra-estruturas monobloco com os das infra-estruturas pós-soldagem (a laser). A partir de dois modelos-mestre, foram enceradas 40 amostras sobre copings pré-fabricados de pilares de implantes tipo Estheticone e Micro-Unit (Conexão Sistema de Prótese-SP). Obteve-se oito infra-estruturas metálicas a partir da fundição das ligas Ni-Cr, Ni-Cr-Ti-Mo, Pd-Ag e Ti-c.p., sendo duas infraestruturas para cada liga. Os valores correspondentes às leituras das distâncias verticais (em !m) da relação infra-estruturas metálicas e pilares de implantes de todas as amostras das diferentes ligas metálicas utilizadas e das etapas monobloco e soldagem a laser foram tabulados e, em seguida, aplicado os testes estatísticos. Os valores foram sujeitos à análise de variância e as médias com diferenças estatísticas significativas foram comparadas pelo teste de Tukey com nível de significância 5% (p<0,05), bem como o desvio padrão. Os resultados evidenciaram que nas infra-estruturas em monobloco (sem solda), houve a presença de desajuste, porém os valores médios não apresentaram diferenças estatísticas significativas. Na avaliação do material empregado (ligas) verificou-se que as infra-estruturas em Ti-c.p. não apresentaram valores médios discrepantes, o que não ocorreu com as infra-estruturas obtidas com as demais ligas. Na comparação de todas as ligas utilizadas, os seus valores médios não apresentaram diferenças estatísticas significativas e a liga de Pd-Ag (Grupo Controle) foi a que apresentou valor médio de maior desajuste nas estruturas em monobloco. Na correlação das infra-estruturas monobloco e pós-soldagem (a laser), evidenciou-se a existência de diferenças estatísticas significativas, baseado nos valores médios (monobloco 0,0953&#956;m / solda a laser 0,0452&#956;m), sendo o desajuste marginal vertical para a infra-estrutura com solda a laser, significativamente menor.

Dans ce travail, nous avons étudié la relaxation de couches d’hétérostructures InGaN/GaN obtenue par épitaxie en phase vapeur aux organométalliques (EPVOM) et épitaxie aux jets moléculaires (EJM) principalement par microscopie électronique en transmission (MET). Pour ce faire, nous avons fait varier la composition de l'indium de 4.1% au nitrure d'indium pur, ce qui correspond lors de la croissance sur GaN à un décalage paramétrique allant de 1% à 11.3%. Le travail a porté sur des couches dont l’épaisseur allait de 7 nm à 500 nm. A partir d’une composition en indium voisine de 10%, nous mettons en évidence la formation d’un réseau de dislocations vis dont la ligne se promène dans l’interface, avec de très longues sections droites le long des directions <11-20>. Ces dislocations coexistent avec un réseau de dislocations coins qui commence à se former vers 13%, il disparait complétement autour d’une composition en indium de 18%. Le réseau de dislocation vis se densifie de plus en plus au-delà. Outre ces dislocations de décalage paramétrique, d'autres mécanismes qui contribuent à la relaxation de la contrainte dans ces hétérostructures InGaN/GaN ont été mis en évidence. Ainsi, au-dessus d'une composition d'indium supérieure à 25%, de nombreux phénomènes se produisent simultanément. (1) Formation des dislocations de décalage paramétrique à l'hétérointerface; (2) une composition de la couche qui s’enrichit en indium vers la surface; (3) des fortes perturbations de la séquence hexagonale conduisant à un empilement aléatoire; (4) croissance à trois dimensions (3D) pouvant même conduire à des couches poreuses lorsque la composition en indium est comprise entre 40% et 85%. Cependant, on met en évidence qu’il est possible de faire croître de l’InN pur de bonne qualité cristalline s'améliore grâce à la formation systématique d'une couche 3D. / In this work, we have investigated the strain relaxation of InGaN layers grown on GaN templates by MOVPE and PAMBE using TEM. To this end we varied the indium composition from 4.1% to pure indium nitride and the corresponding mismatch was changing from less than 1% to 11.3%, the thickness of the InGaN layers was from 7 nm to 500 nm. When the indium composition is around 10%, one would expect mostly elastically strained layers with no misfit dislocations. However, we found that screw dislocations form systematically at the InGaN/GaN interface. Moreover, below 18% indium composition, screw and edge dislocations coexist, whereas starting at 18%, only edge dislocations were observed in these interfaces. Apart from the edge dislocations (misfit dislocations), other mechanisms have been pointed out for the strain relaxation. It is found that above an indium composition beyond 25%, many phenomena take place simultaneously. (1) Formation of the misfit dislocations at the heterointerface; (2) composition pulling with the surface layer being richer in indium in comparison to the interfacial layer; (3) disruption of the growth sequence through the formation of a random stacking sequence; (4) three dimentional (3D) growth which can even lead to porous layers when the indium composition is between 40% and 85%. However, pure InN is grown, the crystalline quality improves through a systematic formation of a 3D layer.

This thesis deals with the Europeanization of the selected Czech social policy actors, among them some trade unions and non-governmental organizations. It examines their changes in some particular areas: in an organizational structure, in financial resources, in activities, in interests, in the used argumentation towards representatives of state power and in attitudes to the cooperation with partners from the other EU countries. These changes are observed thanks to the country's accession to the EU and/or thanks to the actors' membership in the European interest groups. The thesis tries to prove that these changes have been caused, at first, by the misfit among the Czech actors and their counterparts from the other EU member states. In the latter case it assesses if it is possible to attribute changes to socialization into the European interest groups. It also focuses on the fact whether there have been suitable conditions for the social learning of the observed actors. The questionnaire and secondary literature have been used for the evaluation. It has been proved that the concept of misfit is not suitable for these cases and thus the observed changes cannot be ascribed to this concept. Another situation occurs when evaluating changes resulting from socialization. There has been shown that the...