This thesis deals with the preparation of chemically and/or enzymatically modified cellulose. This modification can be either irreversible or reversible. Irreversible modification is used to prepare cellulose derivatives as end products, whereas reversible modification is used to enhance solubility in the preparation of regenerated cellulose. The irreversible modification studied here was the preparation of carboxymethyl cellulose (CMC) using extended mercerization of a spruce dissolving pulp. More specifically the parameters studied were the effect of mercerization at different proportions of cellulose I and II in the dissolving pulp, the concentration of alkali, the temperature and the reaction time. The parameters evaluated were the degree of substitution, the filterability and the amount of gel obtained when the resulting CMC was dissolved in water. Molecular structures of CMC and its gel fractions were analysed by using NIR FT Raman spectroscopy. It was found that the alkali concentration in the mercerization stage had an extensive influence on the subsequent etherification reaction. FT Raman spectra of CMC samples and their gel fractions prepared with low NaOH concentrations (9%) in the mercerization stage indicated an incomplete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Low average DS values of the CMC, i.e. between 0.42 and 0.50 were obtained. Such CMC dissolved in water resulted in very thick and semi solid gum-like gels, probably due to an uneven distribution of substituents along the cellulose backbone. FT Raman spectra of CMC samples and their gel fractions mercerized at higher alkaline concentration, i.e. 18.25 and 27.5% in the mercerization stage, indicated on the other hand a complete transformation of cellulose to Na-cellulose before carboxymethylation to CMC. Higher average DS values of the CMC, i.e. between 0.88 and 1.05 were therefore obtained. When dissolved in water such CMC caused gel formation especially when prepared from dissolving pulp with a high fraction of cellulose II. The reversible modification studied was the dissolution of cellulose in NaOH/ZnO. Here the effect of enzyme pretreatment was investigated by using two mono-component enzymes; namely xylanase and endoglucanase, used in consecutive stages. It was found that although the crystallinity and the specific surface area of the dissolving pulp sustained minimal change during the enzymatic treatment; the solubility of pulp increased in a NaOH/ZnO solution from 29% for untreated pulp up to 81% for enzymatic pretreated pulp. / Baksidetext Cellulose can be chemically and/or enzymatically modified. Irreversible modification is used to prepare cellulose derivatives as end products, reversible modification to enhance solubility in the preparation of regenerated cellulose. The irreversible modification studied here was the preparation of carboxymethyl cellulose (CMC) using extended mercerization of a spruce dissolving pulp. More specifically the parameters studied were the effect of mercerization at different proportions of cellulose I and II in the dissolving pulp, the concentration of alkali, the temperature and the reaction time. It was found that the alkali concentration in the mercerization stage had an extensive influence on the subsequent etherification reaction. The content of cellulose II had little effect on degree of substitution (DS) at low NaOH concentration, but tended to decrease DS at higher NaOH concentration in both cases compared with cellulose I. It was also found that the content of cellulose II correlates with the gel formation obtained when the CMC is dissolved in water. The reversible modification studied was the dissolution of cellulose in NaOH/ZnO. Here the effect of enzyme pretreatment was investigated by using two mono-component enzymes; namely xylanase and endoglucanase, used in consecutive stages. It was found that the solubility of pulp increased in a NaOH/ZnO solution from 29% for untreated pulp up to 81% for enzymatic pretreated pulp.

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.

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.

[pt] Resinas epóxi do éter diglicidílico de bisfenol A (DGEBA) são amplamente usadas como matriz de materiais compósitos. No entanto, o principal monômero utilizado para a sua produção, o Bisfenol A (BPA), apresenta significativos efeitos negativos na saúde humana. Implicações ambientais que limitam o uso BPA fazem necessária a substituição dos monômeros base para a preparação de resinas epóxi por outros mais seguros e ambientalmente sustentáveis. Por outro lado, resinas epóxi preparadas a partir de fontes renováveis constituem uma alternativa ao uso de resinas derivadas do petróleo na produção de materiais compósitos. Assim, óleos naturais derivados de fontes vegetais são considerados uma matéria-prima alternativa para a obtenção de resinas epóxi de base biológica por causa da sua disponibilidade e uma ampla variedade de possibilidades para transformações químicas. Além disso, materiais compósitos fabricados a partir de resinas termo-endurecíveis de origem vegetal e fibras lignocelulósicas como material de reforço, poderiam contribuir com a produção sustentável de materiais de baixo custo e menor densidade que possuam propriedades estruturais funcionais. Neste trabalho propõe-se a preparação de laminados utilizando como matriz resinas epóxi biobaseadas obtidas a partir de óleo de soja epoxidado e cardanol epoxidado (proveniente da casca de castanha de caju) e fibras lignocelulósicas de bucha (Luffa cylindrica) como reforço. Os efeitos estruturais, morfológicos e térmicos de tratamentos superficiais de hornificação, mercerização e acetilação nas fibras foram estudados usando espectroscopia no infravermelho por transformada de Fourier (FTIR), difração de raios X (DRX), microscopia eletrônica de varredura (MEV), microscopia de força atômica (AFM) e análise termogravimétrica (TGA). Compósitos DGEBA/Bucha e Resina natural/Bucha foram fabricados pelo método lay-up manual e suas propriedades mecânicas foram avaliadas por meio de ensaios de flexão em três pontos e da técnica não destrutiva de excitação por impulso (TEI). Esta técnica também foi utilizada para a determinação experimental dos módulos dinâmicos e das propriedades de amortecimento dos compósitos durante o envelhecimento por UV e por absorção de água. O comportamento dinâmico-mecânico dos compósitos foi avaliado por meio da análise dinâmico-mecânica (DMA). Resinas preparadas com 50 por cento de cardanol epoxidado e 50 por cento de resorcinol curadas com diamina de isoforona apresentaram melhores propriedades térmicas e mecânicas, comparados com sistemas com óleo de soja epoxidado, com uma temperatura de transição vítrea média de 74 graus Celsius e módulo de armazenamento de 880,5 MPa, constituindo uma alternativa mais sustentável para a fabricação de materiais compósitos pela substituição do sistema bisfenol A clássico analisado também neste trabalho, com valores Tg igual a 77,5 graus Celsius e E linha igual a 849 MPa. A adição de fibras de bucha em forma de manta permitiu a obtenção de compósitos com modos de fratura controlada. Além disso, foi observada uma melhora na aderência na interfase fibra-resina em compósitos com 30 por cento de fibras de bucha mercerizada. / [en] Diglycidyl ether of bisphenol A (DGEBA) currently represents the most widely used type of epoxy resin in the world in several applications. However, the main monomer used for its production, Bisphenol A (BPA) is considered an endocrine disruptor with estrogenic activity that has significant negative effects on human health. Environmental implications and laws limiting the use of BPA in several countries make it necessary to replace the base monomers for the preparation of epoxy resins with safer and more environmentally sustainable ones. Epoxy resins prepared from renewable sources are an alternative to the use of petroleum resins in the production of composite materials. Thus, natural oils derived from vegetable sources are considered as an alternative raw material for obtaining biologically based epoxy resins because of their availability, their relatively low price and a wide variety of possibilities for chemical transformations. On the other hand, composite materials made from thermosetting resins of vegetable origin and lignocellulosic fibers as reinforcement material could contribute to the sustainable production of low cost and lower density materials that have functional structural properties. This work proposes the preparation of composite materials, using biobased epoxy resins obtained from epoxidized soybean oil and epoxidized cardanol from cashew nuts as well as lignocellulosic (Luffa cylindrica) fibers modified by surface treatments of hornification, mercerization and acetylation. The structural, morphological and thermal effects of surface treatments on the fibers were studied using Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). DGEBA/Luffa and Biobased resin/Luffa fiber composites were fabricated by the manual lay-up method and their mechanical properties were evaluated by three-point bending tests and the non-destructive impulse excitation technique (TEI). This technique was also used for the experimental determination of the dynamic modules and the damping properties of the laminates obtained during UV aging and water absorption. The effect of the introduction of the binder fibers and the different treatments performed on the fibers on the dynamic-mechanical behavior of the composites was performed by dynamic-mechanical analysis (DMA). Resins prepared with 50 percent epoxidized cardanol and 50 percent resorcinol cured with isophorone diamine presented better thermal and mechanical properties, compared to systems with epoxidized soybean oil, with an average glass transition temperature of 74 degrees Celsius and a storage modulus of 880, 5 MPa, constituting a sustainable alternative for the manufacture of composite materials by replacing the classic bisphenol A system also analyzed in this work, with values Tg equal to 77.5 degrees Celsius and E line equal to 849 MPa. The addition of luffa fibers allowed the production of composites with controlled fracture modes. In addition, an improvement in the fiber-resin interface adhesion was observed in composites with 30 percent mercerized fibers.