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Analysis and synthesis of degree of articulation /Wouters, Johan, January 2001 (has links)
Thesis (Ph. D.)--Oregon Graduate Institute, 2001.
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Analysis and synthesis of degree of articulation /Wouters, Johan, January 2001 (has links)
Thesis (Ph. D.)--Oregon Graduate Institute, 2001. / Includes bibliographical references (leaves 97-105).
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The synthesis and analysis of water soluble rigid-rod polyelectrolyteKuo, Chien-Hung 01 August 2000 (has links)
Development of opto-electronic polymers has been focused on conjugated rigid-rod polymers which assume a para-catenated backbone yielding a rod-like configuration. As a consequence of their rigidity, the rod-like molecules display superior mechanical properties, thermo-oxidative stability and solvent resistance. The later two characters cause difficulties in processing these high-performance rigid-rod polymers. This in terms limits their applications in critical technologies, such as conducting polymers, nonlinear optics, and solid polyelectrolytes.
In this study, chemical derivatives of the rigid-rod polymers were synthesized using pendants of propane-sulfonated ionomers to (1) enhance the solubility of the rigid-rod polymers, and (2) generate a solid polyelectrolyte suitable for energy storage. Extensive synthesis efforts were focused on generating monomers and polymers of propane-sulfonated poly(p-phenylene-benzobisimidazole), PBI, making it a water soluble electrolyte. Various analysis techniques were applied to ascertain the chemical structure and the purity of the monomers and of the polymers. The polymer molecular weight was also determined using viscometry. An intrinsic viscosity of 4.9 dL/g was achieved for the 2-sulfo-PBI and of 0.58 dL/g for the propane-sulfonated PBI with Na+ ionomer pendants
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Synthesis and characterisation of transition metal fluoridesBlack, Cameron January 2015 (has links)
This thesis reports exploratory studies on the synthesis of new vanadium and copper-containing compounds, with a particular emphasis on preparing new magnetically-active materials with S = ½ spin configurations. Eighteen crystal structures are reported, sixteen of which represent new compounds. These materials were studied for magnetic behaviour where appropriate. The sixteen vanadium-containing compounds were prepared using either the hydrothermal, Solvothermal or ionothermal synthesis methods at temperatures ranging from 60 °C to 200 °C. Inorganic cations and organic moieties were used as templating agents to direct the structures, often targeting potentially frustrated lattices based on triangular motifs by using ‘triangular' templating molecules such as guanidine. Solvent choices, as well as reactant ratios were all varied in order to produce the new oxide, fluoride and oxyfluoride compounds of vanadium. Three families of vanadium compounds were prepared from these methods; a family of 1D vanadium (IV) oxyfluoride ladder compounds of general formula AVOF₃ (A=K⁺, Rb⁺, Cs⁺ or NH₄⁺), and a family of 1D vanadium fluoride chain compounds of general formula A₂VF₅ (A=K⁺ or NH₄⁺). The third family is comprised of three vanadium-containing compounds of varying dimensionality that share guanidine as the common organic moiety. Several miscellaneous compounds of vanadium such as clusters and a new V (IV) layer were synthesized, and are reported. The two copper compounds containing compounds, analogous to the pseudo-kagome compound, Cu₃Bi(SeO₃)₂O₂Br, were prepared via solid-state techniques. A detailed neutron diffraction study was carried out on the two compounds to measure the evolution of the magnetic properties from room temperature down to 2.5 K. Representational analysis was utilised in order to provide a detailed magnetic model of the compounds.
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A complementary study of perovskites : combining diffraction, solid-state NMR and first principles DFT calculationsJohnston, Karen Elizabeth January 2010 (has links)
Perovskites, ABX₃, and their associated solid-solutions are a particularly important and attractive area of research within materials chemistry. Owing to their structural and compositional flexibility and potential physical properties they are one of the largest classes of materials currently under investigation. This thesis is concerned with the synthesis and structural characterisation of several perovskite-based materials using a combined approach of high-resolution synchrotron X-ray and neutron powder diffraction (NPD), solid-state Nuclear Magnetic Resonance (NMR) and first-principles Density Functional Theory (DFT) calculations. Initial investigations concentrated on room temperature NaNbO₃, a perovskite widely debated in the literatue. Published crystallographic data indicate NaNbO₃ possesses two crystallographically distinct Na sites in space group Pbcm. Whilst some of our materials appear in agreement with this (notably a commercially purchased sample) many of our laboratory-synthesised samples of NaNbO₃ routinely comprise of two phases, which we show to be the antiferroelectric Pbcm and polar P2₁ma polymorphs. Several different synthetic methods were utilised during this investigation and the quantity of each phase present was found to vary as a function of preparative method. ²³Na, ⁹³Nb and ¹⁷O DFT calculations were used in conjunction with experiment to aid in spectral analysis, assignment and interpretation. In addition, ab initio random structure searching (AIRSS) was utilised in an attempt to predict the most stable phases of NaNbO₃. This proved to be both successful and highly informative. A series of NaNbO₃-related solid-solutions, namely K[subscript(x)]Na[subscript(1-x)]NbO₃ (KNN), Li[subscript(x)]Na[subscript(1-x)]NbO₃ (LNN) and Na[subscript(1-x)]Sr[subscript(x/2)]□[subscript(x/2)]NbO₃ (SNN) have also been synthesised and characterised. The substitution of K⁺ , Li⁺ and Sr²⁺ cations onto the A site appears to produce the same polar P2₁ma phase initially identified in the room temperature NaNbO₃ investigation. The abrupt change in cation size in the KNN and LNN series, and the introduction of vacancies in the SNN series, is thought to result in a structural distortion which, in turn, causes the formation of the P2₁ma phase. A low temperature synchrotron X-ray powder diffraction study (12 < T < 295 K) was completed for a sample of NaNbO₁ composed of the P2₁ma polymorph (~90%) and a small quantity of the Pbcm phase (~10%). A region of phase coexistence was identified between the P2₁ma, R3c and Pbcm phases over a relatively large temperature range. Full conversion of the P2₁ma phase to the low temperature R3c phase was not possible and, consistently, the P2₁ma phase was the most abundant phase present. Factors such as structural, strain, crystallite size and morphology are thought to be crucial in determining the exact phases of NaNbO₃ produced, both at low and room temperature. The solid-solution La[subscript(1-x)]Y[subscript(x)]ScO₃ was also investigated. Compositions x = 0, 0.2, 0.4, 0.6, 0.8 and 1 were successfully synthesised and characterised. Refined high-resolution NPD data indicates that an orthorhombic structure, in space group Pbnm, was retained throughout the solid-solution. Using ⁴⁵Sc and ⁸⁹Y MAS NMR each sample was found to exhibit disorder, believed to result from both a distribution of quadrupole and chemical shifts. NMR parameters were calculated for several model Sc and Y compounds using DFT methods to determine the feasibility and accuracy of ⁴⁵Sc and ⁸⁹Y DFT calculations. These proved successful and subsequent calculations were completed for the end members LaScO₃ and YScO₃. DFT calculations were also utilised to gain insight into the disorder exhibited in the La[subscript(1-x)]Y[subscript(x)]ScO₃ solid-solution.
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Psychological therapy in prisons : professionals' perceptionsVölker, Faye Tameryn January 2016 (has links)
No description available.
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Continuity of care and its effect on patients' motivation to initiate and maintain cardiac rehabilitationPayne, Liz January 2015 (has links)
Background: Despite national guidance and empirical support for its clinical and cost-effectiveness, cardiac rehabilitation (CR) is underused. Only 44% of patients go to CR, with angioplasty (Percutaneous Coronary Intervention; PCI) patients being least likely to attend (31% of 87,000). Aim: To investigate the relationship between ‘continuity of care’ and patients’ motivation towards CR, through the lens of self-determination theory, and develop a model to inform service design to increase CR uptake and adherence. Methods: A mixed methods approach was used. In Study 1, a theoretical model of continuity of care and motivational antecedents was tested with a cross-sectional sample of 107 PCI patients. To further explore interactions between continuity of care and motivation towards cardiac rehabilitation, a Critical Interpretive Synthesis of the extant literature was used in Study 2, and focus groups were carried out with patients and service providers in Study 3. Results: In Study 1, continuity of care positively predicted patients’ autonomous motivation towards CR, and this was partially mediated by autonomy support. Autonomy support was associated with CR attendance. In Studies 2 and 3, aspects of continuity of care with positive effects on attendance were identified. These included timely, appropriate information provision, relationships bridging CR phases and settings, and continuing management strategies incorporating trusting, warm staff-patient relationships, and positive encouragement and feedback about progress. The SDT constructs of autonomy support, need satisfaction, internalisation and quality of motivation helped to explain positive and negative influences of continuity on attendance. Conclusion: Continuity of care has a positive effect on patients’ motivation towards CR. The most enduring motivation comes from delivering continuity of care in an autonomy-supportive and competence-supportive way. Longitudinal research is needed to compare how need-supportive and need-thwarting aspects of continuity of care affect CR attendance and adherence, and whether these relationships are influenced by need satisfaction and need frustration.
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Building a prosodically sensitive diphone database for a Korean text-to-speech synthesis systemYoon, Kyuchul, January 2005 (has links)
Thesis (Ph. D.)--Ohio State University, 2005. / Title from first page of PDF file. Document formatted into pages; contains xxii, 291 p.; also includes graphics (some col.) Includes bibliographical references (p. 210-216). Available online via OhioLINK's ETD Center
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Synthesis and structure-property relationships in selected metal fluoridesReisinger, Sandra A. January 2012 (has links)
There has been an increase in the interest in fluoride materials over the last decade. This interest has focused on multiferroic materials and kagome lattices, to name but a few areas. This thesis focuses on the synthesis and crystallographic characterisation of selected transition metal fluorides and oxyfluorides. Work is presented on the tetragonal tungsten bronze solid solutions of KₓFeF₃, where x = 0.58 and x ≈ 0.5, and the copper analogue, K₃Cu₃Fe₂F₁₅; the kagome structure of Cs₂ZrCu₃F₁₂; and hydrothermal reactions using vanadium, manganese, or molybdenum as the transition metals in the formation of new fluorides and oxyfluorides. The tetragonal tungsten bronze compounds KₓFeF₃ (x = 0.58 and x ≈ 0.5) are both tetragonal at 500 K. In the variant with the lower K-content, there is a clear phase separation into two tetragonal phases even at this temperature. The K₀.₅₈FeF₃ sample separates into two distinct phases below 340 K to possess one tetragonal and one orthorhombic phase. Then at roughly 300 K, both samples undergo a phase transition where the tetragonal phase in the P4/mbm space group in K₀.₅₈FeF₃ changes to an orthorhombic phase with a larger unit cell; and the tetragonal phase in P4₂bc for the K₀.₅FeF₃ sample changes to the same orthorhombic model, whilst the P4/mbm model remains unchanged. The evolution of the lattice parameters and phase fractions is studied in detail using synchrotron powder X-ray diffraction (sPXRD). The kagome structure investigated, Cs₂ZrCu₃F₁₂, possesses the “ideal” kagome lattice at room temperature, but previous work has suggested that there is a phase transition at 225 K. The two structures are determined by single crystal X-ray diffraction at 300 K and 125 K. Variable temperature sPXRD studies are performed between these two temperature ranges to determine the phase evolution as a function of temperature. The structure changes from a rhombohedral to a monoclinic phase at low temperature. This is the result of the buckling of the kagome layers at the phase transition. The Zr⁴⁺ ion changes from 6 to 7 coordinate and this is seen as the main driving force for the distortion of the kagome layer from its “ideal” planar arrangement. ii The phase transition is first-order as seen from the electrical impedance measurements. The hydrothermal reactions presented reveal seven new materials and their crystal structures. Sr₂V₂F₁₀·H₂O is new and found to be isostructural to Sr₂Fe₂F₁₀·H₂O. BaVO₂F₃ is a cubic material that is potentially piezoelectric. Two hybrid organic inorganic manganese compounds are reported. The ladder structure (C₃N₂H₅)[Mn₂F₆(H₂O)₂] crystallises in a polar space group and shows promise as a candidate for multiferroic studies. The second hybrid material, (C₇NH₁₆)₂[MnF₅(H₂O)]·2H₂O, crystallises in a centrosymmetric space group. The Mo hybrid materials are all centrosymmetric and possess isolated molybdenum-centred monomeric or dimeric octahedral units.
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Étude de l'apparence physique de surfaces opaques, analyse photométrique et reconstruction 3D / Study of opaque surface physical appearance, photometric analysis and 3D reconstructionTauzia, Emmanuelle 30 June 2016 (has links)
L'étude de l'apparence de surfaces par analyse photométrique est un domaine de recherche actif, avec de nombreuses applications par exemple pour étudier de la qualité de surfaces, la rugosité des objets, leur apparence, etc. Le sujet de cette thèse concerne plus particulièrement l'étude de surfaces opaques, par l'acquisition de la géométrie et de la réflectance. Cela nous a conduit à une analyse des modèles mathématique de réflectance, permettant de représenter les matériaux. Afin d'offrir une description physiquement plausible des matériaux opaques, notre première contribution principale concerne la mise en oeuvre d'un modèle à base de microfacettes Lambertiennes interfacées. Il généralise différents modèles de la littérature incluant des surfaces planes diffuses ou spéculaires et rugueuses diffuses ou spéculaires grâce à trois paramètres physiques : couleur, rugosité et indice de réfraction. Il permet de prendre en compte la transmission des flux lumineux pénétrant sous la surface ainsi que les réflexions multiples entre microfacettes et de restituer les effets de rétrodiffusion lumineuse et d’anisotropie. Notre seconde contribution principale concerne la réalisation d'un système complet d'acquisition de la géométrie et de la réflectance d'objets à partir d'images HDR. Notre méthodologie correspond à une chaîne de reconstruction complète et automatique, uniquement à partir d'images, permettant d'obtenir un niveau de précision intéressant et un faible coût de mise en place et de temps de traitement comparé aux méthodes existantes. Notre méthode permet d'extraire des échantillons de réflectance suffisamment nombreux pour identifier les paramètres de modèles de réflectance avec les données acquises. / The study of surface appearance by photometric analysis is an active area of research, with various applications concerning the analysis of surface roughness or appearance ... The subject of this PhD dissertation relates to the study of opaque surfaces, through the acquisition of their geometry. Our study leads us to an analysis of mathematical reflectance models, for representing materials appearance. To provide a physically plausible description of opaque surfaces, the first major contribution concerns the implementation of a model based on Lambertian interfaced microfacets. This model generalizes several approaches often referenced in the literature, and includes flat diffuse or specular surfaces as well as diffuse or specular microfacets with three physically-based parameters: color, roughness and refractive index. It makes it possible to take into account the transmission of the light flux entering below the surface as well as multiple reflections between microfacets, while handling backscattering and anisotropy. The second main contribution of this work concerns the impolementation of a complete acquisition system for estimating geometry and reflectance from HDR images. Our methodology is based on a complete and automatic reconstruction framework, achieving a higher level of precision, a lower cost of implementation and a shorter processing time compared to photometry-based existing methods.
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