The introduction of a nanoscopic reinforcing phase to a polymer matrix offers great possibilities of obtaining improved properties, enabling applications outside the boundaries of traditional composites. The majority of the work in this thesis has been devoted to polymer/clay nanocomposites in coating applications, using the hydroxyl-functional hyperbranched polyester Boltorn® as matrix and montmorillonite clay as nanofiller. Nanocomposites with a high degree of exfoliation were readily prepared using the straightforward solution-intercalation method with water as solvent. Hard and scratch-resistant coatings with preserved flexibility and transparency were obtained, and acrylate functionalization of Boltorn® rendered a UV-curable system with similar property improvements. In order to elucidate the effect of the dendritic architecture on the exfoliation process, a comparative study on the hyperbranched polyester Boltorn® and a linear analogue of this polymer was performed. X-ray diffraction and transmission electron microscopy confirmed the superior efficiency of the hyperbranched polymer in the preparation of this type of nanocomposites. Additionally, an objective of this thesis was to investigate how cellulose nanofibers can be utilized in high performance polymer nanocomposites. A reactive cellulose “nanopaper” template was combined with a hydrophilic hyperbranched thermoset matrix, resulting in a unique nanocomposite with significantly enhanced properties. Moreover, in order to fully utilize the great potential of cellulose nanofibers as reinforcement in hydrophobic polymer matrices, the hydrophilic surface of cellulose needs to be modified in order to improve the compatibility. For this, a grafting-from approach was explored, using ring-opening polymerization of ε-caprolactone (CL) from microfibrillated cellulose (MFC), resulting in PCL-modified MFC. It was found that the hydrophobicity of the cellulose surfaces increased with longer graft lengths, and that polymer grafting rendered a smoother surface morphology. Subsequently, PCL-grafted MFC film/PCL film bilayer laminates were prepared in order to investigate the interfacial adhesion. Peel tests demonstrated a gradual increase in the interfacial adhesion with increasing graft lengths. / QC20100621

O interesse na utilização de fibras naturais com matrizes poliméricas para a preparação de compósitos espalhou-se rapidamente ao longo dos últimos anos. No entanto, a adesão interfacial entre a fibra e a matriz tem ainda de ser aperfeiçoada. Para melhorar a adesão entre os constituintes e, consequentemente as propriedades mecânicas e térmicas dos materiais, duas abordagens foram investigadas: a irradiação por feixe de elétrons e a mercerização. Este trabalho descreve a fabricação e caracterização de biocompósitos de polietileno de alta densidade e fibra do ouriço da castanha do Brasil que foram preparadas por duas metodologias diferentes: a primeira foi irradiar o compósito com 150 kGy e a segunda foi irradiar a matriz com 15 kGy e então produzir o compósito. Para ambas as metodologias foram utilizadas fibras naturais mercerizadas e não mercerizadas. O efeito dos tratamentos estudados para melhorar a adesão entre a fibra e a matriz polimérica foi avaliado através de caracterizações mecânica, química, térmica e morfológica. Com base neste estudo, observou-se que a fibra do ouriço da castanha do Brasil é um material tecnicamente viável para uso como reforço em compósitos poliméricos. Observou-se que o processo de irradiação da matriz seguida da produção dos compósitos é um método eficaz para melhorar as propriedades térmicas e mecânicas dos compósitos biopoliméricos e que, quando comparado com o processo de mercerização, esse método pode ser considerado mais ambientalmente correto (sem produtos químicos e sem geração de resíduo), mais barato e mais simples. / The interest in the use of natural fibres with polymeric matrix for the preparation of composite spread rapidly over the last years. However, the interfacial adhesion between the fiber and the matrix has to be improved. To improve the adhesion between the constituents and consequently the mechanical and thermal properties of materials, two approaches were investigated: electron beam irradiation and mercerization. This paper describes the fabrication and characterization of biocomposites compounds with high density polyethylene and fibre from Brazil nut pod that were prepared by two different methods: the first irradiating the composite with 150 kGy and the second was radiating matrix with 15 kGy and then produce the composite. For both methodologies, natural fibers, mercerized and non-mercerized were used. The effect of the treatments to improve adhesion between the fiber and the polymer matrix was evaluated through mechanical, chemical, thermal and morphology charcterization. Based on this study, it was observed that fibre from Brazil nut pod is a technically viable material for use as reinforcement in polymer composites. It was observed that the process of matrix irradiation followed by the composite fabrication is an effective method for improving the thermal and mechanical properties of the composites, when compared with mercerization process, this method can be considered more environmentally friendly (no chemicals, and without generating waste), cheaper and simpler.

In present study, high energy electrons were used to modify blends based on RP and PP under two conditions: stationary and in-stationary conditions. Modification of blend under stationary condition is a process which is established in industrial application and where required absorbed dose is applied to form parts (after molding) at room temperature and in solid state. On the contrary, the modification of blend with high energy electrons under in-stationary condition is a new process (electron induced reactive processing) where required absorbed dose is applied to a molten state during melt mixing process. The modification of blend based on RP and PP under stationary condition resulted in slightly enhancement of tensile properties while the modification of this blend under in-stationary condition resulted in deterioration of tensile properties due to degradation of the PP matrix. Thus, special grafting agent (GA) is required for improving the tensile properties. The effect of different GAs on tensile, thermal, dynamic mechanical as well as morphological properties and melt flow properties of blends based on RP and PP were determined. The optimum absorbed dose for modification of blend based on RP and PP under both conditions was evaluated. In addition, the effect of treatment parameters of electron induced reactive processing was investigated.