The preparation of photocrosslinkable bioadhesives synthesized from oligomers of lactic acid and polycaprolactone (PCL), both functionalized with 2-isocyanoethyl acrylate (AOI), were studied. The obtained modified macromers of LA-AOI (mLA) and PCL-AOI (mCL) were chemically characterized by 1H NMR and used to formulate polymeric blends with different mass proportions, 1:1, 1:2 and 2:1, respectively. Subsequently, the produced blends were crosslinked, considering two UV irradiation times: 30 and 120 s. After their production, the thermal and mechanical properties of bioadhesives were assessed, where upon the rheology, gel content, hydrolytic degradation and dynamic contact angles were determined. Furthermore, the cytotoxic profile of bioadhesives was evaluated in contact with human dermal fibroblasts cells, whereas their antibacterial effect was studied monitoring Escherichia coli and S. aureus growth. Overall, flexible and resistant films were obtained, presenting promising features to be used as surgical bioadhesives.

Nesta Dissertação foi realizado um estudo sobre a tenacificação do poliestireno com diferentes tipos de polibutadieno (alto cis, baixo cis e copolímeros dibloco e tribloco de estireno e butadieno). Esses materiais (poliestireno de alto impacto HIPS) foram produzidos por processo de mistura física no estado fundido. Foi realizado um estudo sobre a interação entre a fase rígida do poliestireno (PS) e a fase elastomérica do polibutadieno baixo ou alto cis (PBb ou PBa) das misturas poliméricas, bem como, o grau de interação dos copolímeros em bloco de estireno butadiêno (SB ou SBS) quando a elas são adicionados, em uma percentagem de 2,5%, como agente compatibilizante. As misturas foram analisadas em microscópio eletrônico de varredura (SEM), microscópio eletrônico de transmissão (TEM) e microscópio de força atômica (AFM). As propriedades mecânicas determinadas foram: dureza Shore D, resistência ao impacto (método Izod) e resistência à tração. As propriedades térmicas foram avaliadas por calorimetria diferencial de varredura (DSC), termogravimetria (TG) e análise termodinâmico-mecânica (DMTA). A espectroscopia de ressonância magnética nuclear (NMR) de baixo campo também foi empregada para determinação dos tempos de relaxação de próton (T1) a fim de identificar a formação de domínios do material a nível molecular. Os resultados mostraram que todas as misturas apresentaram um comportamento pseudoplástico. As análises morfológicas indicaram uma morfologia bifásica com domínios de polibutadieno em torno de 1 m de diâmetro, distribuídos aleatoriamente na matriz do poliestireno. Os resultados obtidos nas análises mecânicas mostraram uma melhoria nas propriedades das misturas processadas com polibutadieno alto cis e compatibilizadas com 2,5% do copolímero dibloco de estireno-butadieno (SB). O resultado obtido na análise termogravimétrica revelou uma melhoria da estabilidade térmica dos materiais. Os resultados das análises de DMTA mostraram duas transições distintas. Um aumento significativo da Tg foi observado quando foi utilizado o PBa, indicando uma interação entre as fases. O resultado da análise de NMR mostra uma organização molecular similar nas misturas (PS/PB) e indica que o melhor agente compatibilizante é o copolímero dibloco (SB).

Poly(3-hydroxybutyrate) (PHB) is a thermoplastic polyester with a great potential owing to its biodegradability, bioreabsorbation and biological synthesis from a renewable source. Despite these characteristics, the applications of this polymer are very restricted due to its poor mechanical properties and thermal instability at temperatures above its melting point (around 175°C). Among the possibilities of improvement of these materials, the development of blends is a relatively fast and inexpensive option. Poly(epsilon-caprolactone) (PCL) is a semi-crystalline polymer that may be used as a biomaterial. It presents good mechanical properties, a low melting point (around 55 °C), and could be a good option to develop PHB blends, maintaining the biodegradability and bioreabsorption properties. The objective of the present work was to obtain blends of PHB and PCL by melting mixture in an internal mixer. The compositions varied from 0 to 30 wt% of PCL. DSC, DMA, and SEM were used to characterize the blends. The blends were found to be imiscible with no indication of interaction either the amorphous or crystalline state. The morphology shows PHB as the matrix and PCL as the dispersed phase.

Given the annual growth in food plastic packaging consumption, it is desirable the existence of raw materials, which are alternative to petroleum, especially those renewable or obtained from industrial byproducts, such as the whey protein isolate (WPI). The present work proposes to evaluate the applicability of WPI and polyvinyl alcohol (PVA) new blends as flexible packaging for food. In order to this, blends of WPI with 10%, 20% and 30% of PVA were developed, aiming to increase the WPI films flexibility. Blends, as well as isolated WPI and PVA films, were characterized regarding the following properties: mechanical (tensile and puncture tests), morphological (Scanning Electron Microscopy – SEM), of interaction (Fourier Transform Infrared – FT-IR), optical (% transmittance), thermal (Thermogravimetric Analysis – TGA and Differential Scanning Calorimetry – DSC), of water vapor permeability, of solubility in water and of interaction with moisture under different water activities and temperatures (water sorption isotherms). The addition of 30% of PVA to WPI matrix produced a blend with lower strength, but with a more ductile behavior, exhibiting a ten times higher elongation when compared to WPI film. The tensile properties obtained for this blend were close to those from low density polyethylene (LDPE). The puncture resistance and the water vapor permeability were not affected by the addition of PVA to the WPI matrix, while solubility in water and optical transmittance were reduced when compared to WPI film. Blends showed glass transition temperature values similar to that from WPI film and a good compatibility between the polymers was indicated by Tg results. The experimental data from water sorption isotherms tests were well adjusted through GAB model and curves showed a more expressive increase of water sorption above water activity (aw) of 0.6. The addition of 30% PVA to WPI made the water sorption process more spontaneous. Through the performed analysis it was possible to conclude that is indicated the addition of 30% of PVA to the WPI matrix in order to obtain a more flexible material without prejudice its water barrier property, as well as, that the application of this blend as flexible packaging is suitable for foods and external environments with aw below 0.90.

Uma blenda de polietileno de alta densidade e polietileno de baixa densidade (PEAD/PEBDL) comumente utilizada em filmes de embalagem foi modificada com argila montmorilonita organofílica comercial para obter nanocompósitos com melhores propriedades de barreira. Amostras com 5 e 7,5% de argila (em massa) foram estudadas em diferentes condições de processamento. Filmes produzidos com os nanocompósitos foram avaliados quanto à dispersão da argila por difração de raio X e Microscopia Eletrônica de Transmissão. As propriedades de barreira dos filmes foram determinadas pelas medições de permeabilidade ao oxigênio e ao vapor d'água. As propriedades mecânicas e ópticas também foram determinadas. Observou-se uma estrutura com a argila parcialmente esfoliada e intercalada. A permeabilidade ao oxigênio diminuiu significativamente enquanto a permeabilidade à água foi pouco influenciada. As propriedades mecânicas e a transparência dos filmes foram pouco alteradas. O modelo de Nielsen foi aplicado para os dados de permeabilidade relativa e demonstrou ser um ótimo recurso para a avaliação do grau de esfoliação da argila para as diferentes amostras, que foram confirmadas pelas análises realizadas em microscopia eletrônica de transmissão

In the present paper we report and discuss the physicochemical properties of novel electrolyte membranes, based on poly(vinylidenefluoride-co-trifluoroethylene), PVdF-TrFE, and poly(vinylidenefluorideco- hexafluoropropylene), PVdF-HFP, co-polymer hosts and the PVdF-TrFE/poly(ethylene oxide (PEO) blend as separators for lithium battery systems. The results have shown that the examined separator membranes, particularly those based on the PVdF co-polymers, are able to uptake large liquid amounts leading to high ionic conductivity values. Tests performed on Li/LiFePO4 and Li/SneC cells have revealed very good cycling performance even at high current rates and 100% of DOD, approaching the results achieved in liquid electrolytes. A capacity fading lower than 0.002% per cycle was observed. Particularly, the Li/LiFePO4 cathode cells have exhibited excellent rate capability, being still able to deliver at 2C above 89% of the capacity discharged at 0.1C. These results, in conjunction with the about 100% coulombic efficiency, suggest very good electrolyte/ electrode compatibility, which results from the high purity and stability of the electrolyte and electrode materials and the cell manufacturing.