<p>The sun provides us daily with large quantities of energy in the form of light. With the world’s increasing demand of electrical energy the prospect of converting this solar light into electricity is highly tempting. In the strive towards mass-production and low cost solar cells, new types of solar cells are being developed, e.g. solar cells completely based on organic molecules and polymers. These materials offer a promising potential of low cost and large scale manufacturing and have the additional advantage that they can be produced on flexible and light weight substrate which opens for new and innovating application areas, e.g. integration with paper or textiles, or as building materials. In polymer solar cells a combination of two materials are used, an electron donor and an electron acceptor. The three dimensional distribution of the donor and acceptor in the active layer of the device, i.e. the morphology, is known to have larger influence of the solar cell performance. For the optimal morphology there is a trade-off between sometimes conflicting criteria for the various steps of the energy conversion process. The dissociation of photogenerated excitons takes place at an interface between the donor and acceptor materials. Therefore an efficient generation of charges requires a large interface between the two components. However, for charge transport and collection at the electrodes, continuous pathways for the charges to the electrodes are required.</p><p>In this thesis, results from morphology studies by atomic force microscopy (AFM) and dynamic secondary ion mass spectrometry (SIMS) of spin-coated blend and bilayer thin films of polyfluorene co-polymers, especially poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-5,5-(4´,7´-di-2-thienyl-2´,1´,3´-benzothiadiazole)] APFO-3, and the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) are presented. It is shown that by varying the blend ratio, the spin.-coating solvent, and/or the substrate, different morphologies can be obtained, e.g. diffuse bilayer structures, spontaneously formed multilayer structures and homogeneous blends. The connection between these different morphologies and the performance of solar cells is also analysed. The results indicate that nano-scale engineering of the morphology in the active layer may be an important factor in the optimization of the performance of polymer solar cells.</p>

The sun provides us daily with large quantities of energy in the form of light. With the world’s increasing demand of electrical energy the prospect of converting this solar light into electricity is highly tempting. In the strive towards mass-production and low cost solar cells, new types of solar cells are being developed, e.g. solar cells completely based on organic molecules and polymers. These materials offer a promising potential of low cost and large scale manufacturing and have the additional advantage that they can be produced on flexible and light weight substrate which opens for new and innovating application areas, e.g. integration with paper or textiles, or as building materials. In polymer solar cells a combination of two materials are used, an electron donor and an electron acceptor. The three dimensional distribution of the donor and acceptor in the active layer of the device, i.e. the morphology, is known to have larger influence of the solar cell performance. For the optimal morphology there is a trade-off between sometimes conflicting criteria for the various steps of the energy conversion process. The dissociation of photogenerated excitons takes place at an interface between the donor and acceptor materials. Therefore an efficient generation of charges requires a large interface between the two components. However, for charge transport and collection at the electrodes, continuous pathways for the charges to the electrodes are required. In this thesis, results from morphology studies by atomic force microscopy (AFM) and dynamic secondary ion mass spectrometry (SIMS) of spin-coated blend and bilayer thin films of polyfluorene co-polymers, especially poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-5,5-(4´,7´-di-2-thienyl-2´,1´,3´-benzothiadiazole)] APFO-3, and the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) are presented. It is shown that by varying the blend ratio, the spin.-coating solvent, and/or the substrate, different morphologies can be obtained, e.g. diffuse bilayer structures, spontaneously formed multilayer structures and homogeneous blends. The connection between these different morphologies and the performance of solar cells is also analysed. The results indicate that nano-scale engineering of the morphology in the active layer may be an important factor in the optimization of the performance of polymer solar cells.

The goal of the work is to study possibilities for the modification of interface in immiscible polymer blends, which determine to a large degree of the blend properties. For this purpose novel coupling agents (named SCA) containing 2-oxazoline, 2-oxazinone, and hydrosilane reactive sites have been prepared. In blends of amino- functional and carboxylic acid terminated polymers the oxazoline and oxazinone units of the SCA react selectively with one of the polymers and, therefore, the SCA should locate at the interface. The remaining hydrosilane sites can now be used for further modification, e.g. for crosslinking. In the thesis we discussed the effect of the SCA on the morphology and thermal and rheological properties of blends based on carboxylic acid terminated polystyrene (PS) and amino-terminated polyamide 12 (PA) or poly(methyl methacrylate) (PMMA). The morphology of the blends and the location of the SCA strongly depends on the processing conditions. The crosslinkability of the interface could be proven by changes in the solubility behavior of the blends.

Made available in DSpace on 2014-12-17T14:07:11Z (GMT). No. of bitstreams: 1 QueremAFA_DISSERT.pdf: 6927049 bytes, checksum: 5fbf755901320194b71aa9dc0dc0b657 (MD5) Previous issue date: 2013-06-07 / Studies indicate that a variation in the degree of crystallinity of the components of a polymer blend influences the mechanical properties. This variation can be obtained by subjecting the blend to heat treatments that lead to changes in the spherulitic structure. The aim of this work is to analyze the influence of different heat treatments on the variation of the degree of crystallinity and to establish a relationship between this variation and the mechanical behavior of poly(methyl methacrylate)/poly(ethylene terephthalate) recycled (PMMA / PETrec) with and without the use of compatibilizer agent poly(methyl methacrylate-al-glycidyl methacrylate-al-ethyl acrylate) (MMAGMA- EA). All compositions were subjected to two heat treatments. T1 heat treatment the samples were treated at 130 ? C for 30 minutes and cooled in air. In T2, the samples were treated at 230 ? C for 5 minutes and cooled to approximately -10 ? C. The variation of the degree of crystallinity was determined by the proportional relationship between crystallinity and density, with the density measured by pycnometry. The mechanical behavior was verified by tensile tests with and without the presence of notches and pre-cracks, and by method of fracture toughness in plane strain (KIC). We used the scanning electron microscopy (SEM) to analyze the fracture surface of the samples. The compositions subjected to heat treatment T1, in general, showed an increase in the degree of crystallinity in tensile strength and a tendency to decrease in toughness, while compositions undergoing treatment T2 showed that the opposite behavior. Therefore, this work showed that heat treatment can give a polymer blend further diversity of its properties, this being caused by changes in the crystal structure / Estudos apontam que uma varia??o no grau de cristalinidade dos componentes de uma blenda polim?rica influencia nas suas propriedades mec?nicas. Essa varia??o pode ser obtida pela submiss?o da blenda a tratamentos t?rmicos que levam a modifica??es da estrutura esferul?tica. O objetivo desse trabalho ? analisar a influ?ncia de diferentes tratamentos t?rmicos na varia??o do grau de cristalinidade e estabelecer uma rela??o entre essa varia??o e o comportamento mec?nico da blenda poli(metacrilato de metila)/poli(tereftalato de etileno) reciclado (PMMA/PETrec) com e sem o uso do agente compatibilizante interfacial poli(metacrilato de metila-almetacrilato de glicidila-al-acrilato de etila) (MMA-GMA-EA). Todas as composi??es foram submetidas a dois tratamentos t?rmicos. No tratamento t?rmico T1 as amostras foram tratadas a 130 ?C por 30 minutos e resfriadas ao ar. No tratamento T2 as amostras foram tratadas a 230 ?C por 5 minutos e resfriadas a aproximadamente 10 ?C. A varia??o do grau de cristalinidade foi verificada pela rela??o de proporcionalidade existente entre cristalinidade e densidade, sendo a densidade medida por picnometria. O comportamento mec?nico foi verificado por ensaios de tra??o, com e sem a presen?a de entalhes e pr?-trincas, e pelo m?todo da tenacidade ? fratura em estado plano de deforma??o (KIC). Utilizou-se a microscopia eletr?nica de varredura (MEV) para analisar a superf?cie de fratura das amostras. As composi??es submetidas ao tratamento t?rmico T1, de uma forma geral, mostraram aumento no grau de cristalinidade, na resist?ncia ? tra??o e uma tend?ncia ? redu??o na tenacidade ? fratura, enquanto que as composi??es submetidas ao tratamento T2 mostraram um comportamento oposto a esse. Portanto, este trabalho mostrou que um tratamento t?rmico pode conferir a uma blenda polim?rica uma diversidade ainda maior de suas propriedades, sendo essa ocasionada pelas mudan?as na estrutura cristalina

Orientador: Prof. Dr. Jean Jacques Bonvent / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Biotecnociência, 2015. / Arcaboucos polimericos sao de interesse crescente no campo da engenharia de tecidos. Alguns biopolimeros tais como PLLA -poli (acido latico) e PCL . poli(¿Ã- caprolactona) tem sido amplamente utilizados na composicao destes arcaboucos devido a sua biocompatibilidade, biodegradabilidade e baixa toxicidade. Alem disso, estes biomateriais precisam ter uma boa adesao celular e proliferacao para serem eficazes na reparacao de tecidos. A fim de evitar a invasao de microorganismos, durante o processo de cicatrizacao, e importante a incorporacao de um agente antimicrobiano, para servir como uma barreira protetora e prevenir a infeccao no local da lesao. Tres tipos de arcaboucos foram desenvolvidos a base de PLLA e PCL, e da blenda PCL/PLA - 50/50. A porosidade das membranas de biopolimero foi controlada pela incorporacao de particulas de cloreto de sodio com determinada faixa de tamanho, como agente porogenico, na solucao polimerica, a qual foi, em seguida, removido apos a evaporacao do solvente, por imersao da membrana para a agua para dissolver o sal. A tetraciclina tem sido incorporados a membrana como um agente antibiotico. A morfologia da membrana, estrutura molecular e incorporacao da tetraciclina foram analisados por microscopia eletronica de varredura (MEV), FTIR e microscopia de fluorescencia. A cinetica de libertacao do farmaco foi investigadam atraves da monitorizacao da concentracao de tetraciclina difundida em solucao de PBS (pH 7,4), por meio de espectroscopia de UV-VIS. Os dados experimentais mostraram que a uma porosidade de cerca de 69% foi obtida. A incorporacao de tetraciclina mostrou ser bastante eficaz e uniforme nos arcaboucos, contudo observa-se melhores resultados no caso de PCL puro. A cinetica de libertacao do farmaco e de primeira ordem para arcaboucos com PLA e PCL, puros. No entanto, no caso da blenda, o processo de libertacao do farmaco nao segue nenhum modelo cinetico estabelecido. Tais resultados sugerem que estes suportes de biopolimero podem ser eficazmente produzida com caracteristicas porosas e com a incorporacao de antibioticos, a fim de promover uma libertacao controlada da droga para o processo de reparo tecidual. / Polymeric scaffolds are of growing interest in the field of tissue engineering . Some biopolymers such as PLA - poly lactic acid and PCL - polycaprolactone have been widely used in the composition of these scaffolds due to their biocompatibility, biodegradability and low toxicity. In addition, these biomaterials need to have a good cell adhesion and proliferation to be effective in tissue repair. Furthermore, the formation of pores in the scaffolds is directly related to a better adhesion of material to the cells. In order to avoid microorganism invasion that during the healing process it is important to incorporate an antimicrobial such as tetracycline, to serve as a protective barrier and prevents infection at the site of the injury. Three types of scaffolds were develop, based on PCL, and their blend 50/50, by means of casting process. The porosity of the biopolymer membranes was controlled achieved by the incorporation of sodium chloride particles of given size, as a porogene agent, into the polymer solution, which was then removed after the solvent evaporation by immersion of the membrane into water to dissolve the salt. Tetracycline has been incorporated into to the membrane as an antibiotic agent. The membrane morphology, molecular structure e incorporation of the tetracycline were analyzed by Scanning Electron Microscopy (SEM), FTIR and Fluorescence Microscopy. The drug release kinetic was investigated by monitoring the concentration of tetracycline that diffused to a PBS solution (pH 7.4), by means of uv-vis spectroscopy. The experimental data showed that a medium porosity, of about 69%, could be reached. The incorporation of tetracycline was found to be quite effective and uniform into the scaffolds, tending to lead to better results in the case of pure PCL. The drug release kinetic is of first order for the pure PLA and PCL scaffold. Nevertheless, in the case of the blend, any of the usual kinetic model could describe the drug release process.Such results suggested these biopolymer scaffolds could be effectively produced with porous characteristics and with incorporation of antibiotics in order to promote a controlled drug liberation for wound healing process.

[pt] Blenda polimérica é a mistura física de dois ou mais polímeros, sem reação química intencional entre os componentes. O objetivo básico é combinar as melhores propriedades de cada componente da blenda que, consequentemente, terá propriedades intermediárias àquelas dos polímeros misturados. As maiores vantagens das blendas são a grande variedade e a versatilidade de suas aplicações, que, somadas à facilidade de processamento, possibilitam a produção dos mais diversos produtos, tornando-as competitivas em relação a outros materiais. Outra finalidade das blendas é otimizar a relação custo/benefício e melhorar a processabilidade de polímeros de alta temperatura. Os materiais utilizados neste trabalho foram o PEAD e a PA12, ambos os polímeros sendo de grande importância industrial. O objetivo do trabalho é produzir blendas poliméricas de PEAD/PA12, avaliar a sua miscibilidade e realizar ensaios para extrair suas propriedades. As blendas foram feitas em três composições: 75/25, 50/50 e 25/75 e foi feita a caracterização mecânica com ensaios de tração e fluência, química com análise FTIR e DRX, reológica e análise por MEV e os resultados foram usados para avaliar a combinação das propriedades dos polímeros puros nestas blendas. / [en] Polymer blend is the physical mixture of two or more polymers without any intentional chemical reaction between the components. The basic goal is to combine the best properties of each blend component that, consequently, will have intermediary properties to those of the polymers used. The biggest advantages of the blends are the great variety and the versatility on their applications that added to the good processability, make possible the production of many products making them competitive in relation to other materials. Another objective of the blends is to optimize the cost/benefit relation and improve the processability of high temperature polymers. The materials used on this work were the HDPE and the PA12, both polymers being of great industrial importance. The interest of this work is to produce HDPE/PA12 blends and evaluate their miscibility and make tests to know their properties. The blends were made in three compositions: 75/25, 50/50 and 25/75 and it was done the mechanical characterization with uniaxial tension and creep behavior, chemical characterization with FTIR analysis and x-ray diffraction, rheology and SEM analysis and the results were used to evaluate the combination of the properties of the neat polymers used in these blends.

Neste estudo foram avaliadas amostras de misturas poliméricas de Policarbonato (PC) e Poli-&#61541;-caprolactona (PCL) em diferentes concentrações após enterro em solo preparado, por períodos variando de uma a doze semanas, seguindo a Norma ASTM G 160 - 03. As amostras, após ficarem enterradas, foram retiradas do solo e analisadas por calorimetria diferencial de varredura (DSC), análise termogravimétrica (TGA), microscopia ótica (MO), microscopia eletrônica de varredura (MEV) e espectrometria de absorção na região do infravermelho com transformada de Fourier (FTIR). Foi observado através de avaliação morfológica que houve degradação nas amostras de PCL puro e na mistura PC/PCL (60/40). Para misturas com menores teores de PCL a degradação não foi significativa no tempo de avaliação sugerido pela norma. Após o tempo de 12 semanas em contato com o solo houve uma redução no teor de cristalinidade das amostras tanto de PCL puro quanto da mistura PC/PCL com 40% de PCL. As variações ocorridas devido à biodegradabilidade não foram suficientes para acarretar perda de resistência térmica nas amostras. Verificou-se que para avaliar a biodegradabilidade de misturas contendo o polímero biodegradável PCL, é necessária uma adaptação da Norma utilizada, aumentando o tempo de enterro das amostras / In this study samples of polycarbonate (PC) and poly(&#61541;- caprolactone (PCL) blends were evaluated in different concentrations after being buried under simulation soil condition, for periods varying from one to twelve weeks, following ASTM G 160 03 methodology. The samples, after being buried, were removed from the soil and analyzed by differential scanning calorimetry (DSC), termogravimetric analysis (TGA), optical microscopy (OM), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). It was observed by morphological evaluation that pure PCL and PC/PCL (60/40) blend have suffered degradation. Blends with lower content of PCL did not shown significant degradation during the period of time suggested at the ASTM methodology. After 12 weeks in contact with soil, pure PCL and PC/PCL blend with 40% of PCL, had a decrease in crystalinity content. The variations in the samples due to biodegradability have not been enough to cause loss of thermal resistance in any of the tested samples. It was verified that to evaluate biodegradability of blends containing biodegradable polymer PCL, it is necessary an adaptation of the ASTM methodology, increasing the time of samples burial

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Morphological development during crystallization of thin films of poly(ethylene oxide) (PEO) / poly(methyl methacrylate) (PMMA) blends has been reported. Studies have focused on the effects of the blend composition, PMMA molecular weight, film thickness, and crystallization temperature on the observed crystal morphology. As the blend composition was varied from 90 to 30 wt% PEO, the crystal morphology varied from spherulites to needles and dendrites. Variation of the crystallization temperature and PMMA molecular weight resulted in similar changes in morphology. A morphological map demonstrating the roles of the experimental controls on the observed crystal morphology has been developed. This map was used as a tool for more detailed studies of the observed morphologies and morphological transitions. The dendritic region of the map (~ 30 = 40 wt% PEO) was studied in detail. Changes in the diffusion length were achieved through variation of the PMMA molecular weight, and were shown to influence the secondary sidebranch spacing. Sidebranch spacing measurements revealed that coarsening of the dendritic microstructure occurred well after the competition between diffusion fields of neighboring dendrite arms vanished, indicating the existence of another coarsening mechanism. These studies of dendritic sidebranching indicate that polymer dendrites develop by mechanisms similar to those in small molecules and metals. A number of in-situ observations of morphological transitions have also been reported, including a dense-branched morphology (DBM)/dendrite transition, a DBM/stacked-needle/needle transition, and a transition from dendrites with 90o sidebranching to dendrites with 45o branching or a dense-branched morphology, both of which grow at 45o to the original dendrite trunk. The DBM/dendrite transition occurred over a range of crystallization temperatures, indicating that the transition is not sharp. Crystal growth rate measurements verified this result. The DBM/stacked-needle/needle transitions demonstrated distinct jumps in the crystal growth rate, indicating a change in the growth mechanism or direction. For the transition involving a change in the growth direction, the effective level of noise (fluctuation) was found to be important in morphological selection. The results of this work have helped to define new directions for the study of crystal morphologies, especially in the areas of spherulite formation and dendritic growth. / Ph. D.