Polymers, by virtue of their chemical composition and molecular architecture, exhibit a diverse range of microstructural features and properties. As thin films, due primarily to effects associated with confinement and interfacial interactions, their properties may be film-thickness dependent. The significance of their thicknessdependent behavior is underscored by the fact that polymer films are of technological interest in areas that include, sensors, catalysts and organic electronics. One challenge associated with the use of thin film polymers is to understand the role of confinement and interfacial interactions on thermally induced transitions, such as vitrification and various morphological transitions. To this end, the work presented in this dissertation focuses on the behavior of thermally induced transitions in two thin film polymer-based systems: (1) an A-b-B diblock copolymer which can undergo a disorder-to-order transitions (ODT), wherein the ordered state exhibits varying geometrical symmetries, depending on the relative volume fractions of the A and B components; (2) an amorphous polymer filled with particles of nanoscale dimensions. The first of three problems examined is the influence of supercritical carbon dioxide (scCO₂) on the order-disorder transition of thin film symmetric A-b-B diblock copolymer systems. We show that the transition (xN)ODT, where x is the energetic A-B Flory-Huggins interaction parameter and N is the total degree of polymerization of the copolymer, of the thin film decreased ~ 20% compared to the bulk; the decrease was more significant in scCO₂ environments. The decrease of (xN)ODT in scCO₂ is contrary to observations in bulk copolymer-scCO₂ systems where the effective A-B interactions are weaker, hence the condition for the transition increases to higher (xN)ODT values. With regard to the second problem, we show for the first time experimentally that nanoparticles induced order into thin films of a symmetric A-b-B diblock copolymer at temperatures below the bulk ODT. Finally, we examine the influence of polystyrene (PS) grafted nanoparticles on the glass transition of PS films of varying molecular weight and thickness. We demonstrate that by controlling spatial distribution of nanoparticles, through driving forces of entropic origin, the glass transition temperature of the film can be changed drastically, as much as tens of degrees.

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One of the major issues facing the coal industry today is the decline in economically recoverable reserves, especially in the Witbank 1 Mpumalanga region of South Africa. This necessitates a critical review of alternate coal sources. One such source was identified as previously discarded and currently arising coal fines. It is well known that great value lies within these fines, but that the high moisture content associated with fine coal leads to thermal inefficiencies, handling problems and increased transport cost. This study will investigate thermal drying as a feasible solution to effectively remove this moisture. During thermal drying coal is fed into a high temperature environment; this can influence the physical and mechanical properties of the coal. The effects include swelling, caking, cracking, loss of water, loss of volatiles, and many more. These effects are investigated by means of thennogravimetric analysis, scanning electron microscopy with a heating stage, proximate analysis and mercury intrusion. Coal samples with an average particle size of 500 um were selected for this study. It was found that: The rate of moisture loss up to temperatures between 150 and 200°C is at a maximum where after the rate declines up to temperatures between 350 and 450°C when primary devolatilisation initiates. No visual changes in the coal are observed up to temperatures between 350 and 450°C. A limited amount of volatiles evolve at a constant rate up to 250°C; this is not significant enough to decrease the calorific value of the coal. Porosity changes in the coal are observed from temperatures as low as 250°C. Thermal drying was found to be a feasible alternative to currently employed drying methods with 150°C selected as the optimal drying temperature. A thermal drying plant is proposed with recommendations for future work needed to realise such a plant. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2010

One of the major issues facing the coal industry today is the decline in economically recoverable reserves, especially in the Witbank 1 Mpumalanga region of South Africa. This necessitates a critical review of alternate coal sources. One such source was identified as previously discarded and currently arising coal fines. It is well known that great value lies within these fines, but that the high moisture content associated with fine coal leads to thermal inefficiencies, handling problems and increased transport cost. This study will investigate thermal drying as a feasible solution to effectively remove this moisture. During thermal drying coal is fed into a high temperature environment; this can influence the physical and mechanical properties of the coal. The effects include swelling, caking, cracking, loss of water, loss of volatiles, and many more. These effects are investigated by means of thennogravimetric analysis, scanning electron microscopy with a heating stage, proximate analysis and mercury intrusion. Coal samples with an average particle size of 500 um were selected for this study. It was found that: The rate of moisture loss up to temperatures between 150 and 200°C is at a maximum where after the rate declines up to temperatures between 350 and 450°C when primary devolatilisation initiates. No visual changes in the coal are observed up to temperatures between 350 and 450°C. A limited amount of volatiles evolve at a constant rate up to 250°C; this is not significant enough to decrease the calorific value of the coal. Porosity changes in the coal are observed from temperatures as low as 250°C. Thermal drying was found to be a feasible alternative to currently employed drying methods with 150°C selected as the optimal drying temperature. A thermal drying plant is proposed with recommendations for future work needed to realise such a plant. / Thesis (M.Ing. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2010

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This thesis investigated the physical properties of the macrolide antibiotics: Erythromycin dihydrate (EM-DH), Roxithromycin monohydrate (RM-MH) and Azithromycin dihydrate (AZM-DH). The abovementioned hydrate compounds were investigated in terms of the hydrate-anhydrate crystal structure stability, dehydration and observed polymorphism under controlled temperature heating programs. Identified hydrate and anhydrate polymorphs were subjected to physical stability testing during controlled storage. EM-DH was characterized by thermal analysis (DSC, TGA), X-ray diffraction, FTIR and microscopy. Dehydration of EM-DH at temperatures of 100, 157 and 200°C (followed by supercooling to 25°C) produced the form (I) anhydrate (Tm =142.9°C), form (II) anhydrate (Tm = 184.7°C ) and amorph (II) (Tg = 118°C) respectively. The attempts to produce amorph (I) from melting (in vicinity of form (I) melt over temperature range 133°C to 144°C) and supercooling was unsuccessful due to the high crystallization tendency of the form (I) melt. Brief humidity exposure and controlled temperature (40°C)/ humidity storage for 4 days (0-96% RH) revealed hygroscopic behaviour for the anhydrate crystal (forms (I) and (II)) and amorph (II) forms. Form (II) converted to a nonstoichiometric hydrate where extent of water vapour absorption increased with increased storage humidity (2.1% absorbed moisture from recorded TGA at 96% RH). Amorph (II) exhibited similar trends but with greater water absorption of 4.7% (recorded with TGA) at 96% RH. The pulverization and sieving process of amorph (II) (at normal environmental conditions) was accompanied by some water vapour absorption (1.1%). A slightly lower absorbed moisture content of 3.3% (from TGA) after controlled 4 days storage at 40°C/ 96% RH was recorded. This suggested some physical instability (crystallization tendency) of amorph (II) after pulverization. The thermally induced dehydration of RM-MH by DSC-TG was evaluated structurally (SCXRD), morphologically (microscopy) and by kinetic analysis. Various kinetic analysis approaches were employed (advanced, approximation based integral and differential kinetic analysis methods) in order to obtain reliable dehydration kinetic parameters. The crystal structure was little affected by dehydration as most H-bonds were intramolecular and not integral to the crystal structure stability. Kinetic parameters from thermally stimulated dehydration indicated a multidimensional diffusion based mechanism, due to the escape of water from interlinked voids in crystal. The hygroscopicity of the forms RM-MH, Roxithromycin-anhydrate and amorph glass (Tg = 81.4°C) were investigated. Roxithromycinanhydrate (crystalline) converted readily to RM-MH which were found to be compositionally stable over the humidity range 43-96%RH. Amorphous glass exhibited increased water vapour absorption with increasing storage humidity (40°C/ 0-96% RH). TG analysis suggested a moisture content of 3.5% at 96% RH after 4 storage days. DSC and powder XRD analysis of stored pulverised amorphous glass indicated some physical instability due to water induced crystallization. Commercial AZM-DH and its modifications were characterized by thermal analysis (DSC, TGA), SC-XRD and microscopy. Thermally stimulated dehydration of AZM-DH occurred in a two-step process over different temperature ranges. This was attributed to different bonding environments for coordinated waters which were also verified from the crystal structure. Dehydration activation energies for thermally stimulated dehydration were however similar for both loss steps. This was attributed to similarities in the mode of H- bonding. Different forms of AZM were prepared by programmed temperature heating and cooling of AZM-DH. The prepared forms included amorphous glass (melt supercooling), amorphous powder (prepared below crystalline melting temperature), crystalline anhydrate and crystalline partial dehydrate. Humidity exposure indicated hygroscopic behaviour for the amorphous, crystalline anhydrate and crystalline partial dehydrate modifications. Both the crystalline anhydrate and partial dehydrate modifications converted to the stoichiometric dihydrate form (AZM-DH) at normal environmental conditions at ambient temperature. Both the amorph glass and amorph powder exhibited increased moisture absorption with increased humidity exposure. TG analysis of the pulverised amorph glass indicated a moisture content of 5.1% at 96% RH after 4 storage days. The absence of crystalline melt in DSC and presence of Tg (106.9°C) indicated the sample remained amorphous after pulverisation and storage for 4 days at 40°C/ 96% RH.

In-situ combustion is an oil recovery technique in which air, or oxygen enriched air is injected into a reservoir in order to displace the oil. Under suitable conditions the oxygen will burn with part of the oil, raising the temperature of the reservoir and reducing the viscosity of the oil, hence allowing it to flow more easily. A serious problem with mathematical modelling of in-situ combustion is that of flame extinction due to grid block size effects. When modelling a field scale process using finite difference techniques the grid block size will be far larger than the flame length. Since parameters such as temperature and saturations are averaged over a grid block they will be misrepresented in the Arrhenius reaction rate equation, and the flame may die out. The approach taken to overcome the problem is to decouple the flame from a conventional finite difference simulator and solve separately for the reaction rate and flame velocity. This is achieved using a steady state analysis that applies a reduced set of the conservation equations in a moving frame over the flame region, and solves the resulting eigenvalue problem using a shooting method. The reaction rate and flame velocity determined by the steady state analysis are then used to apply the 'thin flame' technique to the conventional simulator. This treats the flame as a moving heat source and displacing pump, travelling through the domain with the velocity obtained by the steady state analysis. The steady - state analysis is compared with experimental results glvmg good agreement for the flame parameters. The thin flame method produces excellent agreement with the conventional simulator on laboratory scale simulations, and on field scale simulations it greatly reduces the problems associated with grid block size effects.

In looking to the future of naval warfare, the US Navy has committed itself to development of future classes of an All-Electric Ship (AES) that will incorporate significant technological advancements in the areas of power management, advanced sensor equipment and weaponry, reconfigurability, and survivability systems while simultaneously increasing overall system efficiencies and decreasing the operational costs of the future naval fleet. As part of the consortium responsible for investigating the viability of numerous next-generation technologies, the University of Texas at Austin is dedicated to providing the capabilities and tools to better address thermal management issues aboard the future AES. Research efforts at the University of Texas in Austin have focused on the development of physics-based, dynamic models of components and subsystems that simulate notional future AES, system-level, thermal architectures. This research has resulted in the development of an in-house thermal management tool, known as the Dynamic Thermal Modeling and Simulation (DTMS) Framework. The work presented herein has sought to increase the modeling capabilities of the DTMS Framework and provide valuable tools to aid both developers and users of this simulation environment. Using numerical approximations of complex physical behaviors, the scope of the DTMS Framework has been expanded beyond elements of thermal-fluid behaviors to capture the dynamic, transient nature of far broader, more complex architectures containing interconnected thermal-mechanical-electrical components. Sophisticated interfacial systems have also been developed that allow integration of the DTMS Framework with external software products that improve and enhance the user experience. Developmental tools addressing customizable presentation of simulation data, debugging systems that aid in introduction of new features into the existing framework, and error-reporting mechanisms to ease the process of utilizing the power of the simulation environment have been added to improve the applicability and accessibility of the DTMS Framework. Finally, initial efforts in collaboration with Mississippi State University are presented that provide a graphical user interface for the DTMS Framework and thus provide far more insight into the complex interactions of numerous shipboard systems than would ever be possible using raw numerical data. / text