The potential applications of dispersed and self-assembled nanoparticles depend critically on accurate control and prediction of their phase behavior. The chemical potential is essential in describing the equilibrium distribution of all components present in every phase of a system and is useful as a building block for constructing phase diagrams. Furthermore, the chemical potential is a sensitive indicator of the local environment of a molecule or particle and is defined in a mathematically rigorous manner in both classical and statistical thermodynamics. The goal of this research is to use simulations and experiments to understand how particle size and composition affect the particle chemical potential of attractive nanoparticle-polymer mixtures. The expanded ensemble Monte Carlo (EEMC) simulation method for the calculation of the particle chemical potential for a nanocolloid in a freely adsorbing polymer solution is extended to concentrated polymer mixtures. The dependence of the particle chemical potential and polymer adsorption on the polymer concentration and particle diameter are presented. The perturbed Lennard-Jones chain (PLJC) equation of state (EOS) for polymer chains1 is adapted to calculate the particle chemical potential of nanocolloid-polymer mixtures. The adapted PLJC equation is able to predict the EEMC simulation results of the particle chemical potential by introducing an additional parameter that reduces the effects of polymer adsorption and the effective size of the colloidal particle. Osmotic pressure measurements are used to calculate the chemical potential of nanocolloidal silica in an aqueous poly(ethylene oxide) (PEO) solution at different silica and PEO concentrations. The experimental data was compared with results calculated from Expanded Ensemble Monte Carlo (EEMC) simulations. The results agree qualitatively with the experimentally observed chemical potential trends and illustrate the experimentally-observed dependence of the chemical potential on the composition. Furthermore, as is the case with the EEMC simulations, polymer adsorption was found to play the most significant role in determining the chemical potential trends. The simulation and experimental results illustrate the relative importance of the particles size and composition as well as the polymer concentration on the particle chemical potential. Furthermore, a method for using osmometry to measure chemical potential of nanoparticles in a nanocolloid-mixture is presented that could be combined with simulation and theoretical efforts to develop accurate equations of state and phase behavior predictions. Finally, an equation of state originally developed for polymer liquid-liquid equilibria (LLE) was demonstrated to be effective in predicting nanoparticle chemical potential behavior observed in the EEMC simulations of particle-polymer mixtures.

Across the world, war has been declared against poverty because of its devastating effects on local communities. The world has made a concerted effort to fight the effects of poverty through developmental agencies and regional integration bodies such as the World Bank, International Monetary Fund (IMF), World Trade Organisation (WTO), United Nations Development Programme (UNDP) and the Southern African Development Community (SADC). In an effort to complement the efforts of the above–mentioned agencies and bodies, the South African government has developed its own poverty alleviation strategies, policies, initiatives and Acts that focus primarily on alleviation of poverty on the level of local government. The Constitution of South Africa, 1996 provides the guidelines to several regulations and Acts (such as the Development and Facilitation Act, 67 of 1995, the Local Government: Municipal Systems Act, 32 of 2000, and the Local Government: Municipal Structures Act, 117 of 1998.) that support the alleviation of poverty on the local sphere of government. The Integrated Development Planning programme was formulated and implemented to alleviate poverty at this level. The purpose of this study was to determine how the level of poverty within the Dr Kenneth Kaunda District Municipality could be alleviated through effective integrated development planning. A quantitative approach was followed because the target population response rate was expected to be large. In addition, the research design for this study included a literature review, analyses of official documents, observation and data sampling through questionnaires and scientific analysis of the responses. The study found that IDP objectives aligned to service delivery targets were unclear and did not depict the aspirations and needs of the community. The programmes aimed at the infrastructure coupled with skills development programmes and job creation initiatives could assist in the alleviation of poverty. / M Development and Management, North-West University, Potchefstroom Campus, 2014

L'objet de cette thèse est d'étudier les liens qui existent entre les déséquilibres macroéconomiques et les crises, et de voir dans quelles mesures leur prise en compte peut aider une meilleure gestion des crises dans les pays de la zone euro. Les différents chapitres de cette thèse tentent d'apporter des réponses à trois questions importantes : Quels sont les indicateurs macro-financiers qui pourraient aider à mieux anticiper les épisodes de stress budgétaire dans les pays de la zone euro ? Quelles seraient les conséquences de la mise en place d'un système de garantie des dépôts bancaires sur les variables macroéconomiques et sur le comportement des investisseurs, investisseurs qui tiendraient compte du risque de défaut souverain ? Dans quelle mesure une meilleure qualité des institutions, de la gouvernance pourrait-elle aider à améliorer la croissance de long terme d'une économie contrainte sur le marché international des capitaux ? En retenant une approche de court terme, les deux premiers chapitres montrent l'importance de la confiance des marchés dans l'analyse du lien entre déséquilibres macroéconomiques et crises. Dans le troisième chapitre, nous adoptons une perspective de plus long terme pour analyser les effets de cette confiance des marchés sur la dynamique de la croissance. Notre approche est à la fois théorique et empirique. L'approche théorique se base sur les modèles DSGE (modèles d'équilibre général stochastiques dynamiques et la modélisation d'une crise dans une petite économie ouverte. L'approche empirique se focalise sur les modèles Probit/Logit sur données de panel et sur un modèle d'alerte fondé sur des signaux avancés (early warning indicators). / This dissertation consists of three essays on how macro-financial imbalances precede crises and to what extent their consideration can help better management of crises in the Eurozone countries. The different chapters of this thesis, try to answer three important questions : What are the macro-financial imbalances that exposed the Euro area countries to fiscal stress before the outbreak of the debt crises in Europe? What are the impacts of sovereign default and deposit guarantee on macroeconomic variables and on the behavior of investors ? To what extent could better institutions/governance help to improve the long-term growth in a constrained economy on the international capital market ? Using a short-term approach, the first two chapters show the importance of market confidence in analysis of the link between macroeconomic imbalances and crises. In the third chapter, we adopt a long-term perspective to analyze the effects of this market confidence on the dynamics of growth. Our approach is both theoretical and empirical. The theoretical approach is based on the DSGE models (dynamic stochastic general equilibrium models) and the modeling of a crisis in a small open economy (SOE). The empirical approach focuses on Probit/Logit models for panel data and on Signal model based on early warning indicators.

Stimuli-responsive (stimuli-sensitive, intelligent, or smart) polymers are polymer materials which, after small external stimuli, evidently change their physical or chemical properties. Smart polymers can be classified according stimuli they respond to such as: temperature changes, mechanical stress, light irradiation, ultrasonic treatment, application of external magnetic as well as electric field, changes of pH, ionic strength, addition of the chemical agents and presence of biomolecules and bioactive molecules. Stimuli-responsive synthetic polymer systems has attracted considerable attention due to wide range of applications, i.e. controlled drug delivery and release systems, diagnostics, tissue engineering and 'smart' optical systems, as well as biosensors, microelectromechanical systems, coatings, and textiles. Among the types of stimuli for this dissertation temperature, pH and reactive oxygen species (ROS) responsive polymer systems were studied. In case of thermoresponsive polymers, when polymer chains are molecularly dissolved in a good solvent, changes (increasing or decreasing) of temperature result in insolubility (globular nanoparticles formation) of polymer chains, called temperature induced phase-separation. pH responsive polymers change properties such as: solubility, volume (gels),...

To minimize global carbon emissions, having efficient jet engines and internal combustion engines necessitates utilizing lightweight alloys such as Al, Ti, and Mg-based alloys. Because of their remarkable strength/weight ratio, these alloys have received a lot of attention. Nonetheless, they have very poor tribological behavior, particularly at elevated temperatures beyond 200 °C, when most liquid lubricants begin to fail in lubrication. Over the last two decades, there has been a lot of interest in protecting Al, and Ti-based alloys by developing multiphase solid lubricants with a hard sublayer that provide mechanical strength and maintain the part's integrity while providing lubricity. The development of novel coatings with superior lubricity, high toughness, and high-temperature tolerance remains a challenging and hot topic to research and provide new engineered solutions for. To address and provide solutions to protect light-weight, i.e., Al, and Ti alloys at high-temperature and bestow superior tribological properties to such alloys, three types of adaptive lubricious coatings have been studied in this thesis: Nb-Ag-O self-healing lubricious ternary oxide, PEO-chameleon a self-adaptive multi-phase coating, and Sb2O3-MSH-C lubricious adaptive coatings to address this challenge. The development of the Nb-Ag-O ternary resulted in a coefficient of friction as low as 0.2 at 600 °C and crack healing at 900 °C. PEO-chameleon coatings demonstrated a remarkably low COF, as low as 0.07 at 300 °C and 1.4 GPa applied pressure. Finally, the Sb2O3-MSH-C multi-phase lubricious solid lubricant revealed superlubricity, with a CoF of 0.008 at 300 °C, providing a potentially promising contender for high-temperature, high-load applications.

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No description available.

Dans le travail actuel, nous avons entrepris une étude structurale des monocristaux de polystyrène-polyoxyde d'éthylène (PS-b-PEO) pour élucider l'influence de la conformation du bloc de PS sur la cristallisation à partir d'une solution diluée. Nous avons également étudié le comportement des monocristaux lors d'une chauffe. Il est à noter que l'intérêt dans ces systèmes a été récemment réapparu en vue d'utilisation des monocristaux de copolymères pour générer des brosses amorphes uniformes. Lors de la cristallisation du PEO le bloc amorphe, c. à d. le PS, est rejeté du cristal et s'accumule donc sur des surfaces basales des lamelles cristallines. Puisque l'épaisseur cristalline qui résulte d'un processus de cristallisation isotherme a une valeur bien définie, la densité de greffage de PS en est aussi. Ainsi en changeant l'épaisseur du cristal nous pouvons générer des brosses de PS ayant des densités de greffage très variées. Dans notre étude, nous avons employé une combinaison des techniques d'analyse qui sont opérationnelles dans l'espace directe et réciproque telles que l'AFM et le SAXS/WAXS. Les expériences AFM ont été réalisées sur des monocristaux isolés tandis que les mesures SAXS/WAXS ont été faites sur des gâteux de monocristaux orientés qui ont été préparés par sédimentation lente à partir d'une solution diluée. L'interprétation des résultants SAXS se base sur le modèle à deux phases où les épaisseurs des régions cristallines (Lc) et amorphes (La) peuvent être déterminées en suivant les approches conventionnelles de la fonction de corrélation ou la fonction de distribution des interfaces. / In the present work, we have undertaken a structural study of PS-b-PEO single crystals to elucidate the influence of the state of the PS block on crystallization from dilute solution and on subsequent thermal annealing at elevated temperature. It is noteworthy that the interest in these systems has been recently renewed in the perspective of using them as a model of grafted amorphous brushes with variable grafting density. Indeed, during crystallization of PEO, the amorphous block, i.e. PS, is rejected from the crystal accumulating on its basal surfaces. Since the crystal thickness formed during isothermal crystallization is a sharply selected value, the grafting density of the resulting PS brush is also well defined. Therefore by varying the crystal thickness one can obtain the PS brushes with grafting density varying in a broad range.In our study, a combination of reciprocal and direct-space techniques such as SAXS/WAXS and AFM was employed. While AFM experiments were performed on isolated single crystals, the SAXS investigation was carried out on oriented mats of single crystals slowly sedimented from the "mother" solution. In this case, the one-dimensional two-phase system model was used for the data interpretation where the thickness of the amorphous (La) and crystalline (Lc) layers are conventionally determined following the correlation fonction and interface distribution fonction approaches.

The existence of hydrodynamically developed, laminar Viscoelastic Secondary Flows (VSFs) of non-Newtonian fluids in straight ducts of non-circular cross-section was proposed in the 1950's. VSFs have since been observed sporadically, and only once with a velocimetric technique. Using axial and transverse full flow-field velocity-position raster maps made with Rheological Nuclear Magnetic Resonance (Rheo-NMR), Newtonian and non-Newtonian fluid flows were quantified in Hagen-Poiseuille and Power Law contexts, over more than two orders of magnitude of flow rate, in ducts of circle, square, triangle, and pentagon cross-section. VSF was reliably and repeatedly observed to occur at between one part in 130 and one part in 600 of the primary axial flow velocity. Velocity measurements ranged from <10 µm/s to approximately 30 cm/s, suggesting a velocity dynamic range >3E4 without optimization. To obtain VSF flow direction information, a novel flow directional phantom was developed and characterized. Aqueous solutions of Polyethylene Oxide (PEO), Viscarin GP-109NF, Viscarin GP-209NF (V209), Hyaluronan (HA) in a Phosphate-Buffered Saline-like solvent, and an aqueous Polyethylene Glycol/PEO-based Boger fluid were investigated. Axial data was corroborated with related data gathered by an independent method. Basic simulations corroborated the VSF observations. Duct hydraulic diameters (>= 1.6 mm) approached the micro-channel regime. VSF detections in HA --- synovial fluid's principal component --- and V209 were novel, as were observations of some artifacts which were subsequently characterized and corrected. The detection of VSF in HA represents the first experimental evidence suggesting that its second normal stress (N_2) is comparable to that of better-characterized fluids. In the first application of a new VSF-based method, a particular Boger fluid's constant viscosity and, in the square duct, its lack of VSF were used with established criteria to suggest that the fluid's N_2 approached zero. The development of a rudimentary, but versatile and inexpensive home-built velocimetric spectrometer is detailed, as are several new components. An exhaustive VSF literature review is included. The remarkable transverse velocimetric ability of Rheo-NMR in both optically opaque and transparent system is highlighted, suggesting that perhaps the technique might represent, in both micro-channels and conventional ducts, the gold-standard in flow velocimetry.

The presented doctoral research was aimed at preparation and characterization of ultra thin polymer films on solid substrates using different physical techniques. Each of these physical techniques probes selectively different characteristics of the films. While some of the techniques are strong in the predetermination of some unique properties of the layers, they might be limited and give no specific/conclusive information about some other important characteristics. Therefore, only the combination of the techniques provides a profound picture of the thickness, architecture, composition and functionality of the films/layers. This combined characterization approach elucidates in details the physical characteristics and the mechanisms responsible for the unique behavior of different polymer films/layers in the application that they are intended for. In the thesis, of particular interest were films of high biomedical, biotechnological and tissue engineering importance, such as: 1. poly(lactide) films formed by grafting "from-" a silanized alacrite thin films (L605 Co-based super alloy), 2. polydopamine (PDA) films that could serve as substrate independent mod- ification platform for further surface modification steps, 3. poly(ethylene oxide)films formed by "grafting to-" PDA modified surfaces, 4....