Les copolymères séquencés amphiphiles sont très prometteurs pour des applications de technologie de pointe en raison de leur capacité à s'auto-assembler dans des structures bien organisées à l'échelle du micro– et du nanométre, et de leur sensibilité à des stimulations de différentes natures. La formation des nanomotifs bien ordonnés dans les films et/ou en masse fournit un substitut à la nanolithographie et est utile pour le design et l'ingénierie de nanomembranes et de matériaux nanoporeux. L'auto–assemblage dans des solvants sélectifs, en incluant la sensibilité au pH et à la température, peut être ajusté pour correspondre aux besoins de différentes applications biomédicales, telles que l’encapsulation et/ou relargage de médicaments, l'ingénierie de tissus, etc. Dans ce contexte, des copolymères séquencés de type L–lactide (LLA) et méthacrylate 2–diméthylaminoéthyl (DMAEMA) sont d’un grand intérêt. Comme le contrôle sur l'auto–assemblage des copolymères séquencés est permis au niveau moléculaire, il est très important de préparer des copolymères bien définis avec des longueurs de bloc prévisibles et de faible polydispersité. Ainsi, une partie de cette étude a été consacrée au développement de procédures synthétiques optimales et à la caractérisation détaillée de copolymères di– et triblocs de LLA et de PDMAEMA. Un outil simple pour déterminer la présence d'homo–PLLA résiduel a été développée; cela a permis de déterminer et d'expliquer plusieurs voies de synthèse indésirables. La dernière inclut la participation possible de l'amorceur bifonctionnel utilisé, et nous avons alors proposé un système alternatif d'amorceur bifonctionnel/catalyseur. La racémisation du LLA par les unités amine de (P)DMAEMA a été observée pendant la polymérisation, limitant ainsi l'utilisation première du bloc PDMAEMA pour la préparation des copolymères PLLA–b–PDMAEMA. Les études thermiques et de cristallisation, en incluant les copolymères séquencés partiellement quaternisés, ont révélé un retard significatif de la vitesse de cristallisation, en présence du bloc de PDMAEMA. Nous avons constaté que les blocs sont miscibles pour de faibles masses molaires et que la miscibilité partielle est maintenue après quaternisation. Selon la longueur et le taux de quaternisation du bloc PDMAEMA, la cristallisation du PLLA a été étudiée dans un environnement restreint et confiné, faiblement ou fortement. La torsion des lamelles cristallines observée pour certains copolymères biséquencés a été accentuée dans les copolymères triséquencés, où la formation de sphérolites annelés a été observée dans toutes les conditions thermiques utilisées. / Multi–functional amphiphilic block copolymers have much promise for various high technology applications thanks to the controlled stimuli–responsive self–assembly into well–organized structures on the micro– and nanometer scales. The formation of well–ordered nanopatterns in films and/or in bulk provides a competitive substitute to nanolithography and is useful in the design and engineering of nanomembranes and nanoporous materials. Solution self–assembly in selective solvents, including pH and temperature sensitivity, can be tuned to match the needs of different biomedical applications, such as drug encapsulation/delivery, tissue engineering, etc. In this context, block copolymers of L–lactide (LLA) and 2–dimethylaminoethyl methacrylate (DMAEMA) are of great interest. Since the control over self–assembly of block copolymer systems is enabled on a molecular level, it is of great importance to prepare well–defined block copolymers with predictable block lengths and low polydispersity. Thus, a major part of the research in this study was devoted to developing optimal synthetic procedures with detailed characterization of linear di– and triblock copolymers of LLA and PDMAEMA. A simple tool to determine homo–PLLA impurity was developed, which helped to determine and explain several undesired routes. The latter includes possible involvement of the bifunctional initiator used, and an alternative bifunctional initiator/catalyst system was proposed. Racemization of LLA by (P)DMAEMA moieties was observed during LLA polymerization thus limiting the utilization of PDMAEMA–first approach for the preparation of PLLA–b–PDMAEMA. Thermal and crystallization studies, including on quaternized block copolymers, revealed a significant retardation effect of the PDMAEMA block on the crystallization kinetics. The blocks were found to be miscible in the melt at low molecular weights, and maintained partial miscibility after quaternization. Depending on the length and the quaternization degree of PDMAEMA, PLLA crystallization was studied in a templated, soft or hard confinement environment. Crystalline lamellae twisting observed in certain diblock copolymers was facilitated in triblock copolymers, where the formation of banded spherulites was observed in all thermal conditions used. / Part of the research described in this thesis is conducted in collaboration with Centre d' étude et de Recherche sur les Macromolécules (CERM), Université de Liège, Sart-Tilman, Belgium

Please read the abstract in the section 00front of this document / Thesis (PhD)--University of Pretoria, 2008. / Materials Science and Metallurgical Engineering / PhD / Unrestricted

This disseration covers the processing and characterization of nanocellulose polymer composites. In this disseration, two fiber spinning methods were developed to create high stiffness nanocomposite fibers from renewably-sourced materials and the properties of these nanocomposites were evaluated. Additionally, bulk nanocomposites were created and some of the properties of these materials, for different types of nanoparticles, are also discussed. Evaluation of nanocellulose as a nucleation agent in poly(lactic acid) is also presented for very small concentrations of nanocelluloses in a plasticized polymer.

Uganda is well endowed with economic quantities of mineral salts present in the interstitial brines and evaporite deposits of Lake Katwe, a closed (endorheic) saline lake located in the western branch of the great East African rift valley. Currently, rudimentally and artisanal methods continue to be used for salt extraction from the lake raw materials. These have proved to be risky and unsustainable to the salt miners and the environment and they have a low productivity and poor product quality. This work involves the investigation of the salt raw materials that naturally occur in the brines and evaporites of Lake Katwe. The purpose is to propose strategies for the extraction of improved salt products for the domestic and commercial industry in Uganda. The literature concerning the occurrence of salt and the most common available technologies for salt extraction was documented. Also, field investigations were undertaken to characterize the salt lake deposits and to assess the salt processing methods and practices. The mineral salt raw materials (brines and evaporites) were characterized to assess their quality in terms of the physical, chemical, mineralogical, and morphological composition through field and laboratory analyses. An evaluation of the potential of future sustainable salt extraction from the lake deposits was done through field, experimental, and modeling methods. Moreover, the mineral solubilities in the lake brine systems and dissolution kinetics aspects were investigated. The results reveal that the salt lake raw materials contain substantial amounts of salt, which can be commercialized to enable an optimum production. The brines are highly alkaline and rich in Na+, K+, Cl-, SO42-, CO32-, and HCO3-. Moreover, they contain trace amounts of Mg2+, Ca2+, Br-, and F-. The lake is hydro-chemically of a carbonate type with the brines showing an intermediate transition between Na-Cl and Na-HCO3 water types. Also, the evaporation-crystallization is the main mechanism controlling the lake brine chemistry. These evaporites are composed of halite mixed with other salts such as hanksite, burkeite, trona etc, but with a composition that varies considerably within the same grades. The laboratory isothermal extraction experiments indicate that various types of economic salts such as thenardite, anhydrite, mirabilite, burkeite, hanksite, gypsum, trona, halite, nahcolite, soda ash, and thermonatrite exist in the brine of Lake Katwe. In addition, the salts were found to crystallize in the following the sequence: sulfates, chlorides, and carbonates. A combination of results from the Pitzer’s ion-interaction model in PHREEQC and experimental data provided a valuable insight into the thermodynamic conditions of the brine and the sequence of salt precipitation during an isothermal evaporation. A good agreement between the theoretical and experimental results of the mineral solubilities in the lake brine systems was observed with an average deviation ranging between 8-28%. The understanding of the mineral solubility and sequence of salt precipitation from the brine helps to control its evolution during concentration. Hence, it will lead to an improved operating design scheme of the current extraction processes. The dissolution rate of the salt raw materials was found to increase with an increased temperature, agitation speed and to decrease with an increased particle size and solid-to-liquid ratio. Moreover, the Avrami model provided the best agreement with the obtained experimental data (R2 = 0.9127-0.9731). In addition, the dissolution process was found to be controlled by a diffusion mechanism, with an activation energy of 33.3 kJ/mol. Under natural field conditions, the evaporative-crystallization process at Lake Katwe is influenced by in-situ weather conditions. Especially, the depth of the brine layer in the salt pans and the temperature play a significant role on the brine evaporation rates. With the optimal use of solar energy, it was established that the brine evaporation flux can be speeded up in the salt pans, which could increase the production rates. Moreover, recrystallization can be a viable technique to improve the salt product purity. Overall, it is believed that the current work provides useful information on how to exploit the mineral salts from the salt lake resources in the future. / <p>QC 20151217</p>

Orientador: Keizo Yukimitu / Banca:João Carlos Silos Moraes / Banca: Valmor Roberto Mastelaro / Banca: Mauro Luciano Baesso / Banca: Tomaz Catunda / Resumo: O desenvolvimento de sistemas e dispositivos ópticos deu origem à área hoje conhecida como fotônica. A busca por novas aplicações ou aprimoramento de sistemas optoeletrônicos tem levado à obtenção de novos materiais vítreos, os quais exigem minuciosa investigação com relação às suas propriedades físicas. Entre os vários sistemas vítreos estudados, os vidros teluritos destacam-se como um dos mais promissores vidros óxidos já desenvolvidos quando comparados com outros vidros clássicos, como os vidros silicatos, fosfatos e boratos. Desta forma, neste trabalho foram preparados vidros com diferentes composições para o sistema Li2O-TeO2-R (R: WO3 e Nb2O5), e caracterizados usando técnicas de análises térmicas, estruturais e ópticas. O estudo das propriedades térmicas é importante na determinação e entendimento do mecanismo de nucleação e crescimento de cristais, sendo, essencial este conhecimento quando o intuito for preparar vidros de alta qualidade exigidos para aplicações tecnológicas. O desenvolvimento tecnológico destes vidros requer que a nucleação intrínseca e o crescimento de cristais sejam suficientemente reduzidos para evitar perdas ópticas. O estudo estrutural destes vidros também é importante para determinação das unidades estruturais constituintes dos vidros. Sabe-se que a adição de metais de transição na matriz telurito provoca a diminuição das unidades TeO3 e aumenta as TeO4, assim, causando aumento da densidade do vidro e, conseqüentemente, aumento no índice de refração. As técnicas utilizadas foram as de análise térmica (DSC), FTIR, XRD, lente térmica (LT) e método de ângulo de Brewster para a obtenção do índice de refração / Abstract: The development of optical systems and devices is the area known as photonics. The search for new applications or improvements of optoelectronic systems has led to the obtaining of new glassy materials, which require thorough investigation with respect to their physical properties. Among the various glass systems studied, the tellurite glasses are presented as one of the most promising oxide glasses that have been developed, when compared with other classics glasses like silicates, phosphates and borates. Thus, in this work were prepared with different glass compositions for the system Li2O-TeO2-R (R: WO3 and Nb2O5) and characterized using techniques of thermal analysis, structural and optical properties. The study of thermal properties is important in determining and understanding the mechanism of nucleation and crystal growth and this knowledge is essential when the purpose is to prepare high-quality glasses required for technological applications. The technological development of these glasses demands sufficiently low intrinsic nucleation and crystal growth to avoid optics losses. The structural study of these glasses is also important for determining the structural units constituting the glass. It is known that the addition of transition metals in the tellurite glass matrix causes a decrease in the TeO3 and increases the TeO4 units and thus causing the increased of density of the glass and, consequently, increasing the refractive index. The techniques used were differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD) and thermal lens (TL) and Brewster angle method for obtaining the refractive index / Doutor

In an effort to minimize the harmful effects of intracellular ice formation (IIF) during cryopreservation of confluent tissues, computer simulations based on Monte Carlo methods were performed to predict the probability of IIF in confluent monolayers during various freezing procedures. To overcome the prohibitive computational costs of such simulations for large tissues, the well-known Johnson-Mehl-Avrami (JMA) model of crystallization kinetics was implemented as a continuum approximation of IIF in tissues. This model, which describes nucleation, growth, and impingement of crystals in a supercooled melt, is analogous to the process of intracellular ice formation and propagation in biological tissues. Based on the work of Weinberg and Kapral (1989), the JMA model was modified to account for finite-size effects, and was shown to predict accurately the results of freezing simulations in 1-D tissue constructs, for various propagation rates and tissue sizes. An initial analysis of IIF kinetics in 2-D tissues is also presented. The probability of IIF in 2-D liver tissue was measured experimentally during freezing of HepG2 cells cultured in monolayers, and compared to Monte Carlo simulations and predictions of the continuum model. The Avrami coefficient and exponent for IIF in HepG2 tissue were estimated to be k = 0.19 and n = 0.45.

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