It is widely recognised that the development and optimisation of industrial processes such as extrusion or injection moulding significantly benefit from accurate polymer processing simulations. Such simulations can lead to enormous cost savings, time to market and product improvements. The development of suitable constitutive models and a robust numerical algorithm are required for successful application of such tool to these processes. Appropriate material characterisation is also imperative to select the constitutive model parameters. Despite the importance and maturity of the polymer processing industry, the constitutive modelling of the rheological behaviour of long chain branched polymers presents still fascinating questions that need some answers. A breakthrough in this area was the design of a constitutive equation based on molecular arguments and known as the pom-pom model. The key feature of this model is the presence of separate relaxation times for the orientation and stretch mechanisms. The pompom model has been proved to be very accurate for the modelling of long chain branched polymers in rheometrical flows. Although very promising, this model suffers from numerical and rheological defects that hinder its use in complex flow simulations. To overcome these issues, the Double Convected pom-pom (DCPP) model is proposed. Its predictive capabilities are first analysed in various rheometrical flows including reverse multi-step shear strain and large amplitude oscillatory shear experiments. For complex flow simulation, the DCPP model is implemented in the commercial package POLYFLOW.Model predictions are compared to experimental birefringence data in planar contraction flows. In all cases, a satisfactory agreement is found between numerical simulation and experiments, demonstrating the potential of this model for the simulation of polymer processing operations. The simulations are then extended to three-dimensional geometries. The influence of non-perfectly two-dimensional flows on birefringence data is analysed. It is shown that the impact of these imperfections is strongly dependent on the flow rate. Is is commonly believed that increasing the geometry aspect ratio tends to decrease three-dimensional influence. It is demonstrated that this is verified only if the zero-order fringe does not disappear at any time during the experiment. Finally, a pragmatic approach is introduced to reformulate constitutive equations to explicitly express them in terms of orientation and stretch variables. This procedure is applied to the Phan-Thien Tanner and Giesekus models and both modelsare compared to the DCPP model. Comparing the models in this form, highlights their differences, and allows one to adopt the best features of each. This almost naturally leads to a proposal of a number of modifications to each of these models. The modified models are then assessed in rheometrical flows by comparing model predictions to experimental data. Significant improvements are demonstrated for in particular the Modified Giesekus model and the Modified DCPP: both models perform remarkably well in a range of non-linear rheometric flows, and are therefore promising candidates for predicting industrial flow problems.

With this research, we work towards the overall objective of customizing polymer molecules in terms of their molecular structure to optimize processing performance. The work includes analysis of the rheology in shear and shear-free flows for sparsely long-chain branched, LCB, polyethylene, PE, resins; determination of the consistency of the molecular based constitutive model, the pom-pom model; for these flows, and evaluation of the same PE resins in film-casting. As we progress towards molecular systems with defined molecular structural characteristics, we transition from a linear low density polyethylene, LLDPE, based series of PE resins to a high density polyethylene, HDPE, based series of PE resins, each with materials of varying degrees of sparse LCB. Evaluation of the shear step-strain rheology for the series of LLDPE-based PE resins allows for the assessment of any inadequacies associated with the step-strain experiments and the ability of the K-BKZ analog of the pom-pom constitutive model to predict step-strain rheological behavior. Finite rise time and wall slip are addressed to ensure the accuracy of the experimental step-strain measurements and eliminated as factors contributing to the stress relaxation moduli response. Analysis of the K-BKZ analog of the pom-pom constitutive model includes comparisons between experimental stress relaxation moduli and predictions from the model using pom-pom model parameters determined from extensional rheology. The results show inconsistencies in the model predictions, where the predictions fail to capture the short time behavior and accurately dampen at larger strains. Pom-pom model parameters are determined using the K-BKZ analog of the pom-pom constitutive model and fitting the stress relaxation moduli. These results are qualitatively consistent indicating that branching occurs on the longest backbone segments, but the values appear to be unrealistic with respect to the molecular theory. Analysis of film-width reduction or necking during film-casting for the series of LLDPE-based resins determines whether uniaxial extensional rheological characteristics, in particular strain-hardening, that are a result of LCB influence the film-necking properties. At the lowest drawdown ratio necking is observed to be reduced with increasing LCB, and thus strain-hardening characteristics. At the higher drawdown ratios it is observed that LCB no longer reduces necking and the curves merge to the results found for linear PE, except in the case of LDPE, which shows reduced necking at all drawdown ratios. Furthermore, comparisons of film necking are also made to separate the effects of molecular weight distribution, MWD, and LCB. The results indicate that both broadening the MWD and the addition of sparse LCB reduce the degree of necking observed. It is established that film necking is more significantly reduced by LCB than by broadening the MWD. Analysis of the uniaxial extensional and dynamic shear rheology with the pom-pom constitutive model reveals that a distribution of branches along shorter relaxation time modes is important in reducing necking at higher drawdown ratios. Factors such as shear viscosity effects, extrudate swell, and non-isothermal behavior were eliminated as contributing factors because of the similar shear viscosity curves, N1 curves, and activation energies among the sparsely LCB PE resins. The same experimental concepts have been extended to the series of HDPE-based resins, but the lack of adequate uniaxial extensional data prevents a thorough analysis with respect to uniaxial extensional characteristics. Regardless, in the context of step-strain rheology, the results were found to be similar with those of the LLDPE-based series of resins, where a distinctive shape at short times was observed for any of the PE resins possessing some level of LCB that was not apparent in the linear PE resins. Film-casting revealed similar results to those of the LLDPE-based materials as well, but a broader spectrum of drawdown ratios revealed greater insight into how the distribution of branching controls the film-casting response. At low drawdown ratios all materials exhibit the same necking behavior. At intermediate drawdown ratios separation occurs where the linear PE resins experiences the most drastic necking, the sparsely LCB PE resins show reduced necking, and the LDPE shows an even greater reduction in necking. Progression then to the higher drawdown ratios results in similar necking behavior for the linear and sparsely LCB PE resins and greatly reduced necking for the LDPE. These results support the idea that to reduce necking the backbone segments that dominate the film-casting behavior must contain some level of LCB. / Ph. D.

This dissertation works towards the larger objective of identifying and assessing the key features of molecular structure that lead to desired polymer processing performance with an ultimate goal of being able to tailor-make specific macromolecules that yield the desired processing response. A series of eight well-characterized, high-density polyethylene (HDPE) resins, with varying degrees of sparse long chain branching (LCB) content, is used to study the effect of both LCB content and distribution on the rheological and commercial processing response using the Pom-pom constitutive relationship. A flow instability known as ductile failure in extensional flow required the development a novel technique known as encapsulation in order to carry out shear-free rheological characterization. Ductile failure prevents the rheological measurement of transient stress growth at higher strains for certain strain-hardening materials. This reduces the accuracy of nonlinear parameters for constitutive equations fit from transient stress growth data, as well as their effectiveness in modeling extensionally driven processes such as film casting. An experimental technique to overcome ductile failure called encapsulation in which the material that undergoes ductile failure is surrounded by a resin that readily deforms homogeneously at higher strains is introduced. A simple parallel model is shown to calculate the viscosity of the core material. The effect of sparse long chain branching, LCB, on the film-casting process is analyzed at various drawdown ratios. A full rheological characterization in both shear and shear-free flows is also presented. At low drawdown ratios, the low-density polyethylenes, LDPE, exhibited the least degree of necking at distances less than the HDPE frostline. The sparsely-branched HDPE resins films had similar final film-widths that were larger than those of the linear HDPE. As the drawdown ratio was increased, film width profiles separated based on branching level. Small amounts of LCB were found to reduce the amount of necking at intermediate drawdown ratios. At higher drawdown ratios, the sparsely-branched HDPE resins of lower LCB had content film-widths that mimicked that of the linear HDPE, while the sparsely-branched HDPE resins of higher LCB content retained a larger film width. Molecular structural analysis via the Pom-pom constitutive model suggested that branching that was distributed across a larger range of backbone lengths serve to improve resistance to necking. As the drawdown ratio increased, the length of the backbones dominating the response decreased, so that the linear chains were controlling the necking behavior of the sparsely-branched resins of lower LCB content while remaining in branched regime for higher LCB content HDPEs. Other processing variables such as shear viscosity magnitude, extrudate swell, and non-isothermal processing conditions were eliminated as contributing factors to the differences in the film width profile. The effect of sparse long chain branching, LCB, on the shear step-strain relaxation modulus is analyzed using a series of eight well-characterized, high-density polyethylene (HDPE) resins. The motivation for this work is in assessing the ability of step-strain flows to provide specific information about a material's branching architecture. Fundamental to this goal is proving the validity of relaxation moduli data at times shorter than the onset of time-strain separability. Strains of 1% to 1250% are imposed on materials with LCB content ranging from zero to 3.33 LCB per 10,000 carbon atoms. All materials are observed to obey time-strain separation beyond some characteristic time, Ï k. The presence of LCB is observed to increase the value of Ï k relative to the linear resin. Furthermore, the amount of LCB content is seen to correlate positively with increasing Ï k. The behavior of the relaxation modulus at times shorter than Ï k is investigated by an analysis of the enhancement seen in the linear relaxation modulus, G0(t), as a function of strain and LCB content. This enhancement is seen to 1) increase with increasing strain in all resins, 2) be significantly larger in the sparsely-branched HDPE resins relative to the linear HDPE resin, and 3) increase in magnitude with increasing LCB content. The shape and smoothness of the damping function is investigated to rule out the presence of wall-slip and material rupture during testing. The finite rise time to impose the desired strain is carefully monitored and compared to the Rouse relaxation time of the linear HDPE resins studied. Sparse LCB is found to increase the magnitude of the relaxation modulus at short times relative to the linear resin. It is shown that these differences are due to variations in the material architecture, specifically LCB content, and not because of mechanical anomalies. / Ph. D.

Polyoxometalates (POMs), which are inorganic metal oxide cluster anions with discrete structures, have been extensively studied in recent years due to their large variety of applications such as medicine, biology, catalysis, material sciences and chemical analysis. Ruthenium polypyridyl complexes have been extensively studied for their applications as photosensitizers in solar energy conversion and photoelectronic materials. Recently, ruthenium heterocyclic ligand complex-based building blocks have been used for the synthesis of hybrid organic-inorganic solids through the self-assembly. We are interested in the synthesis of ruthenium polypyridyl complexes and polyoxometalate anions through different ways such as coordination bonds, hydrogen bonds and ionic bonds to form hybrid organic-inorganic solids. Here, we report four novel hybrid organicinorganic compounds, [Ru(2,2¡¦-bpy)3]2[SiW12O40] (1), [Ru(2,2¡¦- bpy)2(CH3CN)2]2[SiW12O40] (2), [Ru(2,2¡¦-bpy)3][W6O19] (3), and [Ru(2,2¡¦- bpy)3]2[Mo8O26]„ª5H2O (4) ), (2,2¡¦-bpy = 2,2¡¦-bipyridine). Compounds 1, 3, and 4 were synthesized under hydrothermal reaction methods and compound 2 was synthesized by room temperature solution method. These solids were characterized by elemental analysis, UV-vis spectroscopy, fluorescence spectroscopy, thermogravimetric analysis, IR spectroscopy, powder X-ray diffraction, and Single crystal X-ray diffraction. X-ray xii crystallographic study showed that the crystal structures of compounds 1, 2, 3 and 4 were constructed by Coulombic forces and supramolecular interactions. These molecular compounds were further connected and formed 3D structure through Cƒ{H„ª„ª„ªOPOM and other weak interactions. Spectroscopic studies demonstrated that electronic communication occurred between POMs and the sensitizers.

It is generally understood that tidal currents ominated the flow field in many submarine canyons, and internal tide may be an order of magnitude more energetic than that of barotropic. The internal tide can be generated and amplified in a marine environment with the strong vertical density interface. The barotropic tides were known to play the dominant role in driving the internal tides at the topographic relief or shelf break.This research tries to look at the mechanisms of internal tides generation and propagation in the Kaoping Submarine Canyon off southwestern Taiwan, using Princeton Ocean Model (POM) with different settings. The model was tested with bottom topography of flat, a slope and real water depth, with and without vertical stratifications. The model settings are grid size 500m, simulate period days, radiation boundary condition at 4 sides. The model forcings are sea level variations at the west side, both semidiurnal tide (M2) and mixed tide (M2+K1) based on OSU tidal model TPXO 6.2. The results suggest that the offshore M2 tidal forcing can generate large internal tidal currents within the canyon with vertical density stratification. The internal tidal currents at the upper-layer of the canyon lag that of lower-layer 3~5 hours. There is no time lag and no amplification of current in the canyon if there is no stratification. There is a transition zone of minimum flow at depth of about 100-200m. Below the interface, the amplitude of semidiurnal internal tidal current increased with water depth in the canyon. The simulated density contours suggest a 120m amplitude vertical fluctuation center at 150m depth, with 5¢J temperature fluctuation. The computed baroclinic energy flux indicates that the energy in lower layer of the canyon is stronger than that of upper layer. The high energy flux appears at the canyon foot and rim, and propagates along the canyon axis landward.

Com a finalidade de estudar as perturbações médias sobre a Plataforma Continental Sudeste (PCSE) causadas pela passagem de uma frente fria durante o verão, obteve-se um estado básico médio de correntes. Esse campo médio foi obtido com o POM (Princeton Ocean Model) através de simulação diagnóstica, seguida por curta rodada prognostica. As correntes modeladas para o verão na Plataforma Continental Sudeste assemelharam-se em alguns aspectos a correntes obtidas em fundeios de correntógrafos realizados pela Diretoria de Hidrografia e Navegação (DHN), e pelo Instituto Oceanográfico da Universidade de São Paulo, durante os projetos Ciculação Oceânica na Região Oeste do Atlântico Sul (COROAS) e Dinâmica do Ecossistema de Plataforma da Região Oeste do Atlântico Sul (DEPROAS), validando os resultados do modelo Durante a passagem da frente fria as correntes invertem em cerca de seis a nove horas após a passagem do sistema frontal por cada região da PCSE. As etapas da subsidência costeira foram modeladas, ocorrendo transporte de deriva do vento em direção à costa, na camada superficial (0-10m), e transporte de compensação ao longo da coluna d\'água, havendo empilhamento de água na região costeira. A força de gradiente de pressão barotrópica desenvolvida implicou na formação e intensificação do jato costeiro em direção a menores latitudes. Durante esse estado transiente associado à passagem do sistema frontal, a Água Tropical aproxima-se da costa em nível sub-superficial, misturando-se com as águas da plataforma continental A porção da Plataforma Continental Sudeste localizada ao sul da Ilha de São Sebastião é a que responde com maior intensidade à passagem do sistema meteorológico frontal. Na direção transversal à costa, predomina o balanço geostrófico, o qual é intensificado durante a passagem da frente fria, enquanto que ao longo da costa as águas são desviadas do referido balanço pela tensão de cisalhamento do vento e pela aceleração local. Em Cananéia, ocorre a maior amplitude de variação do nível do mar, que pode estar associada a um mecanismo de ressonância entre os ventos do sistema frontal e Ondas de Plataforma Continental geradas pelo vento, uma vez que possuem velocidades de propagação próximas. A plataforma continental adquire vorticidade relativa ciclônica durante a passagem da frente fria. / In order to study the pertubations caused on the South Brazil Bigth (SBB) caused by the passage of a cold front during Summer, a mean basic state for currents was obtained using the POM (Princeton Ocean Model) through diagnostic simulation, followed by a short round prognostic. The mean currents modeled are in certain instancies similar to the currents measured by meter moorings deployed by the Directorate of Hydrography and Navigation (DHN), and by Oceanographic Institute of the University São Paulo during the Projects Oceanic Circulation in the Western South Atlantic (COROAS) and Dynamic of the Ecosystem of the Shelf of the Western South Atlantic Region (DEPROAS), validating results model. During the cold front passage, the currents invert six to nine hours after the passage of the frontal system through each region of the SBB. The stages of coastal subsidence were modeled, with coastward wind drift transport at superficial layer and offshore compensation transport throughout the water column, with piling of water in the coastal region. The strength of the barotropic pressure gradient developed caused the formation and intensification of a coastal jet. During this transient stage associated with the passage of the frontal system, the Tropical Water approaches the coast within sub-surface layer, mixing with continental shelf waters. The portion of SBB located to the South of São Sebastião Island is the portion which is most influenced by the passage of the frontal system. In a normal direction to the coast, the geostrophic balance predominates, being intensified during the passage of the cold front, while along the coast, the waters is diverted from this balance by the wind stress and by the local acceleration, which tend to have opposite signs. Near Cananéia, there is the highest sea level elevation, which may be associated with a mechanism of resonance between the winds of the frontal system and the Continental Shelf Waves generated by the wind, since they have the same speed of propagation. The continental shelf acquires cyclonic relative vorticity during the passage of the cold front.

Com a finalidade de estudar as perturbações médias sobre a Plataforma Continental Sudeste (PCSE) causadas pela passagem de uma frente fria durante o verão, obteve-se um estado básico médio de correntes. Esse campo médio foi obtido com o POM (Princeton Ocean Model) através de simulação diagnóstica, seguida por curta rodada prognostica. As correntes modeladas para o verão na Plataforma Continental Sudeste assemelharam-se em alguns aspectos a correntes obtidas em fundeios de correntógrafos realizados pela Diretoria de Hidrografia e Navegação (DHN), e pelo Instituto Oceanográfico da Universidade de São Paulo, durante os projetos Ciculação Oceânica na Região Oeste do Atlântico Sul (COROAS) e Dinâmica do Ecossistema de Plataforma da Região Oeste do Atlântico Sul (DEPROAS), validando os resultados do modelo Durante a passagem da frente fria as correntes invertem em cerca de seis a nove horas após a passagem do sistema frontal por cada região da PCSE. As etapas da subsidência costeira foram modeladas, ocorrendo transporte de deriva do vento em direção à costa, na camada superficial (0-10m), e transporte de compensação ao longo da coluna d\'água, havendo empilhamento de água na região costeira. A força de gradiente de pressão barotrópica desenvolvida implicou na formação e intensificação do jato costeiro em direção a menores latitudes. Durante esse estado transiente associado à passagem do sistema frontal, a Água Tropical aproxima-se da costa em nível sub-superficial, misturando-se com as águas da plataforma continental A porção da Plataforma Continental Sudeste localizada ao sul da Ilha de São Sebastião é a que responde com maior intensidade à passagem do sistema meteorológico frontal. Na direção transversal à costa, predomina o balanço geostrófico, o qual é intensificado durante a passagem da frente fria, enquanto que ao longo da costa as águas são desviadas do referido balanço pela tensão de cisalhamento do vento e pela aceleração local. Em Cananéia, ocorre a maior amplitude de variação do nível do mar, que pode estar associada a um mecanismo de ressonância entre os ventos do sistema frontal e Ondas de Plataforma Continental geradas pelo vento, uma vez que possuem velocidades de propagação próximas. A plataforma continental adquire vorticidade relativa ciclônica durante a passagem da frente fria. / In order to study the pertubations caused on the South Brazil Bigth (SBB) caused by the passage of a cold front during Summer, a mean basic state for currents was obtained using the POM (Princeton Ocean Model) through diagnostic simulation, followed by a short round prognostic. The mean currents modeled are in certain instancies similar to the currents measured by meter moorings deployed by the Directorate of Hydrography and Navigation (DHN), and by Oceanographic Institute of the University São Paulo during the Projects Oceanic Circulation in the Western South Atlantic (COROAS) and Dynamic of the Ecosystem of the Shelf of the Western South Atlantic Region (DEPROAS), validating results model. During the cold front passage, the currents invert six to nine hours after the passage of the frontal system through each region of the SBB. The stages of coastal subsidence were modeled, with coastward wind drift transport at superficial layer and offshore compensation transport throughout the water column, with piling of water in the coastal region. The strength of the barotropic pressure gradient developed caused the formation and intensification of a coastal jet. During this transient stage associated with the passage of the frontal system, the Tropical Water approaches the coast within sub-surface layer, mixing with continental shelf waters. The portion of SBB located to the South of São Sebastião Island is the portion which is most influenced by the passage of the frontal system. In a normal direction to the coast, the geostrophic balance predominates, being intensified during the passage of the cold front, while along the coast, the waters is diverted from this balance by the wind stress and by the local acceleration, which tend to have opposite signs. Near Cananéia, there is the highest sea level elevation, which may be associated with a mechanism of resonance between the winds of the frontal system and the Continental Shelf Waves generated by the wind, since they have the same speed of propagation. The continental shelf acquires cyclonic relative vorticity during the passage of the cold front.

Cette thèse traite de dédoublement cinétique, de fonctionnalisation et d’utilisation de composés chiraux dérivés de polyoxométalates lacunaires de structure Dawson [α1-P2W17O61]10¬-. La première partie traite de l’utilisation de complexes organosolubles TBA5K[α1-Hf-P2W17O61] pour catalyser l’addition de nucléophiles comme des ethers d’énol ou des acétals de cétènes silylés mais également des pronucléophiles sur des hémiaminals. La seconde partie détaille l’étude sur la préparation et l’utilisation de trichlorostannanes énantiopures en vue du dédoublement cinétique des composés chiraux lacunaires [α1-P2W17O61]10-¬. La fonctionalisation diastéréosélective de derive chiraux organosoluble TBA7[α2-RSnP2W17O61] est également présentée. Le dernier chapitre décrit des hybrides chiraux POM-imidazolidinones dont la chiralité est uniquement apportée par le polyanion. Utilisé avec succès pour catalyser de manière énantiosélective des réactions de Diels Alder, ces composés sont les premiers POM de structure chirale a transféré la chiralité de manière aussi efficace vers des composés organiques. / This manuscript deals with the kinetic resolution, the functionalization and the use of chiral lacunary Dawson α1-POM [α1-P2W17O61]10-¬. The first part deals with the racemic organo-soluble TBA5K[α1-Hf-P2W17O61] complex used to catalyze the nucleophilic addition of silyl enol ethers, ketene-acetals and activated methylene C-nucleophiles onto hemiaminals. The second part describes the synthesis of enantiopure trichlorostannane complexes as resolving agents for the kinetic resolution of chiral [α1-P2W17O61]10-¬. The diastereoselective functionalization of organosoluble chiral TBA7[α2-RSnP2W17O61] is also reported. The final chapter describes chiral POM imidazolidinones hybrids based on the known chiral α1-Dawson POM. Successfully applied as asymmetric catalysts in Diels-Alder reactions, these compounds are the first intrinsically chiral POM to efficiently transfer chirality to organic products.

Approved for public release; distribution in unlimited. / Numerical ocean modeling usually composes various initial- and boundary-value problems. It integrates hydrodynamic and thermodynamic equations numerically with atmospheric forcing and boundary conditions (lateral and vertical) from initial states of temperature, salinity and velocity. Past observations, historical datasets and climatological datasets of the ocean have contributed greatly to the knowledge of the data fields of initial condition, atmospheric forcing and boundary conditions. Change in either initial or boundary condition leads to a variety of model solutions. It is necessary to specify realistic initial and boundary conditions to achieve better understanding and prediction of the ocean behavior. However, uncertainty often exists in both initial and boundary conditions. Up to now, most studies on ocean predictability have usually been for one particular type of model input uncertainty within the three types of uncertainty (initial conditions, open boundary conditions, atmospheric forcing function). This thesis investigates the response of ocean model to the three types of model input uncertainty simultaneously using Princeton Ocean Model (POM) implemented for the Japan/East Sea (JES). / Lieutenant Commander, Taiwan, R.O.C. Navy

>Magister Scientiae - MSc / The motivation to determine H2O2 lies in the fact that this chemical species plays a crucial role in diverse fields of practise such as cosmetic, food, diagnostic, pharmaceutical, clinical and environmental protection industries. Several methods such as chromatography, colorimetry, titrimetry and spectrophotometry have been developed for its detection. However, these methods are known to manifest underlying disadvantages such as high cost, time consuming, instability and complicated immobilization procedures. In this present study an enzyme-less electrochemical sensor based on Ag-Fe2O3/POM/RGO nanocomposite (POM stands for polyoxometalate and RGO stands for reduced graphene oxide) was successfully synthesised via a hydrothermal method and a photochemical reduction method for the detection of hydrogen peroxide (H2O2).