Design and characterization of novel biopolymeric structure using biocompatible ionic liquids

The main objective of this thesis was the development of polymeric structures from the dissolution of FucoPol, a bacterial exopolysaccharide (EPS), in a biocompatible ionic liquid, choline acetate. The FucoPol was produced by the bacteria Enterobacter A47 using glycerol as carbon source at controlled temperature and pH (30ºC and 7, respectively). At the end of 3 days it was produced 7 g/L of FucoPol. The net yield of Fucopol in glycerol (YP/S) was 0.22 g/g and the maximum productivity 2.37 g/L.d This polymer was characterized about its composition in sugars and acyl groups (by High-Performance Liquid Chromatography - HPLC), containing fucose (35 % mol), galactose (21 % mol), glucose (29 % mol), rhamnose (3% mol) and glucuronic acid (12% mol) as well as acetate (14.28 % mol), pyruvate (2.15 % mol) and succinate (1.80 % mol). Its content of water and ash was 15% p/p and 2% p/p, respectively, and the chemical bonds (determined by Infrared Spectroscopy - FT-IR) are consistent to the literature reports. However, due to limitations in Differential Scanning Calorimetry (DSC) equipment it was not possible to determine the glass transition temperature. In turn, the ionic liquid showed the typical behavior of a Newtonian fluid, glass transition temperature (determined by DSC) -98.03ºC and density 1.1031 g/cm3. The study of chemical bonds by FT-IR showed that amount of water (8.80%) influenced the visualization of the bands predicted to in view of their chemical structure. After the dissolution of the FucoPol in the ionic liquid at different temperatures (50, 60, 80 and 100 ° C) it was promoted the removal of this by the phase inversion method using deionized water as a solvent, followed by drying in an oven at 70 ° C. The mixtures before and after the phase inversion method were characterized through the studies mentioned above. In order to explore possible application field’s biocompatibility assays and collage on balsa wood tests were performed. It was found that the process of washing with water by the phase inversion method was not totally effective in removing the biocompatible ionic liquid, since all FucoPol – IL mixtures still contained ionic liquid in their composition as can be seen by the DSC results and FT-IR. In addition, washing the mixtures with water significantly altered the composition of FucoPol. However, these mixtures, that developed a viscous behavior typical of a non-Newtonian fluid (shear-thinning), have the potential to be applied in the biomedical field as well as biological glues.

Proposta e avaliação termodinâmica de soluções para o aproveitamento da exergia na regaseificação de GNL

Uma vez que o gás natural liquefeito (GNL) é transportado a uma temperatura criogénica de -162 °C e como os gasodutos recebem o gás natural (GN) à temperatura ambiente, existe neste sistema exergia que pode ser usada na produção de energia elétrica. A presente dissertação consiste na proposta, avaliação e comparação termodinâmica de diferentes ciclos para produção de energia elétrica, através do aproveitamento da exergia do GNL, aquando da sua transformação em GN, para introdução nos gasodutos. Neste trabalho, considerou-se como caso de estudo o terminal de GNL de Sines, em Portugal, que atualmente não tem implementada nenhuma solução para o aproveitamento da exergia disponível. Considerando os critérios de projeto, definidos de acordo com as características do terminal de Sines e, usando água do mar como fonte de calor, simularam-se e compararam-se os seguintes tipos de ciclos: o ciclo existente no terminal (CE), sem produção de energia; o ciclo de expansão direta do GN (CED); os ciclos tipo Rankine (CTR); os ciclos tipo Rankine com expansão direta (CTR+ED); e os ciclos tipo Rankine com apoio de energia solar (CTRS). Consideraram-se sete fluidos de trabalho (FT) diferentes: propano, etano, etileno, dióxido de carbono, R134a, R143a e propileno. As potências líquidas máximas obtidas para cada ciclo demonstram que: com o CE gastam-se cerca de 1182 kW para fazer o processamento de GNL; com o CED é possível gastar apenas 349 kW; com os CTR é possível obter uma potência líquida positiva ao processar o GNL, produzindo até 2120 kW (usando propileno como FT); com os CTR+ED é possível produzir 2174 kW (também usando propileno com FT); e com os CTRS é possível produzir até 3440 kW (valor médio anual) (usando etano como FT). Fez-se a otimização multi-objetivo dos ciclos tendo-se considerado alguns aspetos económicos. Além da maximização da potência líquida, para os CED, CTR e CTR+ED minimizou-se a área de transferência de calor total dos permutadores de calor e para os CTRS minimizou-se a área de coletores solares instalada.

Geopolymers as infill material for conservation of azulejos

The restoration materials currently used to fill gaps in architectural historical azulejos (e.g. lime or organic resin pastes) usually show serious drawbacks in terms of compatibility, effectiveness and durability. The existing solutions do not fully protect azulejos in outdoor conditions and frequently result in further deterioration. Geopolymers can be a potential solution for azulejo lacunae infill given the chemical-mineralogical similitude to the ceramic body, and also the durability and versatile range of physical properties that can be obtained through the manipulation of their formulation and curing conditions. This work presents and discusses the viability of the use of geopolymeric pastes to fill lacunae in azulejos or to act as “cold” cast ceramic tile surrogates reproducing missing azulejo fragments. The formulation of geopolymers, namely the type of activators, the aluminosilicate source, the amount of water (to meet adequate workability requirements) and curing conditions were studied. The need for post-curing desalination was also considered envisaging their application in the restoration of outdoor architectural historical azulejos frequently exposed to adverse environmental conditions. The possible advantages and disadvantages of the use of geopolymers in the conservation of azulejos are also discussed. Several techniques were used to study the chemical and physical behavior of geopolymers, namely FT-IR, XRD, MIP, SEM-EDS, WDXRF, electrical conductivity, open porosity, bending strength, adhesion strength, water vapour permeability, thermal expansion and hydric expansion. The results indicate that geopolymers are a promising material for restoration of azulejos, exhibiting some properties, such as adhesion to the ceramic substrate, higher than inorganic materials used nowadays, such as aerial lime based pastes.