Orientador: Nelson Eduardo Durán Caballero / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T20:45:34Z (GMT). No. of bitstreams: 1 Ridolfi_DanielaMissiani_D.pdf: 3264748 bytes, checksum: faea0a4fec50e345e79d3072a773bb48 (MD5) Previous issue date: 2014 / Resumo: Neste trabalho nanofibras de quitosana/poli (óxido de etileno) (PEO) (5:1) com nanocristais de celulose (NCC) foram produzidas com sucesso por eletrofiação e foi verificado o efeito da adição dos NCC nas propriedades das nanofibras obtidas. Os ensaios de eletrofiação foram realizados com amostras de NCC obtidas por hidrólise ácida. A eletrofiação de soluções de quitosana, sem e com NCC, resultaram na formação de muitas gotas (beads). Portanto, foi necessário adicionar o PEO nas soluções. Embora a adição de PEO tenha favorecido a formação de fibras, as soluções de quitosana/PEO sem NCC geraram também gotas enquanto que as soluções de quitosana/PEO contendo NCC resultaram em fibras uniformes. As soluções de quitosana/PEO com NCC apresentaram maior viscosidade em relação à solução sem NCC, o que pode ter favorecido a formação de fibras uniformes. As soluções de quitosana/PEO contendo 10% (m/m) de NCC produziram fibras mais finas em relação às soluções com 5% (m/m) de NCC provavelmente devido à maior condutividade da solução. Análises termogravimétricas mostraram que os NCC interferem na decomposição do PEO, mas sem prejudicar o desempenho do material. As nanofibras de quitosana/PEO contendo NCC apresentaram menor cristalinidade em relação às nanofibras sem NCC. Resultados de ensaios com células em culturas de fibroblastos 3T3 mostraram que as nanofibras de quitosana/PEO (com 10% de NCC) promoveram a adesão celular e mantiveram a morfologia celular característica o que sugere um potencial dessas nanofibras para aplicações em engenharia de tecidos / Abstract: In this work chitosan/ poly (ethylene oxide) (PEO) (5:1) nanofibers with cellulose nanocrystals (CNC) were successfully produced by the electrospinning technique and the effect of the addition of CNC on the nanofibers properties was evaluated. The electrospinning assays were performed with samples of CNC obtained by acid hydrolysis. The electrospinning of chitosan solutions, with and without CNC, resulted in the formation of many drops (beads). Therefore, it was necessary to add PEO on solutions. Although the PEO addition has favored the fiber formation, the chitosan/PEO solutions without CNC showed beads while chitosan/PEO solutions with CNC resulted in uniform fibers. The chitosan/PEO solutions with CNC showed higher viscosity compared to the solution without CNC, which may have favored the formation of uniform fibers. Solutions of chitosan/PEO containing 10% (w/w) of CNC produced thinner fibers compared to solutions containing 5% (w/w) of CNC probably due the higher solution conductivity. Thermogravimetric analysis (TGA) showed that the CNC has an effect on the PEO decomposition, however, it does not impair the performance of the material. The chitosan/PEO nanofibers with CNC showed lower crystallinity compared the nanofibers without CNC. Results from cell assay in cultures of 3T3 fibroblasts showed that the chitosana/PEO nanofibers (with 10% of CNC) promoted cell attachment and maintained the characteristic cell morphology which suggests potential applications of these nanofibers in cell tissue engineering / Doutorado / Físico-Química / Doutora em Ciências

This work investigates the compositional and nanostructural variability of celluloses isolated from plants and the impact of the variability in the production of cellulose nanocrystals. A variable set of cellulose isolated from plants were generated starting with a range of feedstocks (coconut fiber, sisal fiber, eucalyptus sawdust, pine sawdust, sugarcane rind and sugarcane pith), applying a range of cellulose isolation processes (acetossolv, liquid hot water, alkaline, and liquid hot water + alkaline) and adding commercial cellulose (eucalyptus kraft pulp, dissolving pulp, and microcrystalline cellulose) as reference materials. The nanostructural characteristics were evaluated by calorimetric thermoporometry, X-ray diffraction, and moisture sorption isotherms. Composition was evaluated by standard wet chemical analysis and insights on functional groups were obtained by infrared spectroscopy. The cellulose nanocrystals were produced by acid hydrolysis with sulfuric acid and characterized by atomic force microscopy and X-ray diffraction. The measured parameters of the isolated celluloses were spread, showing we could achieve a highly diverse set of substrates. Significant correlations between measured variables across the sample set, indicating possible unforeseen multivariate relations among cellulose features. For example, we could show that cellulose monolayer hydration is determined by both hemicelluloses content (compositional parameter) as well as cellulose crystal width (structural parameter). Cellulose nanocrystals were successfully produced, although in some cases such as for the acetossolv pulps the acid conditions were too aggressive and oxidized the substrates. Finally, some quantitative correlations were seen between the parameters of cellulose substrates and the resulting cellulose nanocrystals. These results supply the first hints about how the nanostructural variability of isolated cellulose can influence the cellulose nanocrystals produced from them. / Este trabalho investiga a variabilidade composicional e nanoestrutural de celuloses isoladas de plantas e o seu impacto na variabilidade na produção de nanocristais de celulose. Um conjunto variável de celuloses isoladas de plantas foi gerado a partir de uma série de matérias-primas (fibra de coco, sisal, serragem de eucalipto, serragem de pinheiro, casca de cana e miolo de cana), aplicando uma série de processos de isolamento de celulose (hidrotérmico, alcalino, hidrotérmico + alcalino e acetosolve) e adicionando celuloses comerciais (polpa kraft de eucalipto, polpa para dissolução e celulose microcristalina) como materiais de referência. As características nanoestruturais foram avaliadas por termoporometria calorimétrica, difração de raios X e isotermas de sorção de umidade. A composição foi avaliada por análise química húmida padrão e os conhecimentos sobre grupos funcionais foram obtidos por espectroscopia de infravermelhos. Os nanocristais de celulose foram produzidos por hidrólise ácida com ácido sulfúrico e caracterizados por microscopia de força atômica e difração de raios-X. Os parâmetros medidos das celuloses isoladas foram distribuídos, demonstrando que poderíamos alcançar um conjunto altamente diversificado de substratos. Correlações significativas entre as variáveis medidas foram observadas em todo o conjunto amostral, indicando possíveis relações multivariadas imprevistas entre as características da celulose. Por exemplo, poderíamos demonstrar que a monocamada de hidratação de celulose é determinada tanto pelo conteúdo de hemiceluloses (parâmetro de composição) quanto pela largura do cristal de celulose (parâmetro estrutural). Os nanocristais de celulose foram produzidos com sucesso, embora em alguns casos, como nas polpas acetosolve, as condições ácidas fossem muito agressivas e oxidassem os substratos. Finalmente, algumas correlações quantitativas foram observadas entre os parâmetros dos substratos de celulose e os nanocristais de celulose resultantes. Estes resultados fornecem as primeiras dicas sobre como a variabilidade nanoestrutural da celulose isolada pode influenciar os nanocristais de celulose produzidos a partir deles.

This work investigates the compositional and nanostructural variability of celluloses isolated from plants and the impact of the variability in the production of cellulose nanocrystals. A variable set of cellulose isolated from plants were generated starting with a range of feedstocks (coconut fiber, sisal fiber, eucalyptus sawdust, pine sawdust, sugarcane rind and sugarcane pith), applying a range of cellulose isolation processes (acetossolv, liquid hot water, alkaline, and liquid hot water + alkaline) and adding commercial cellulose (eucalyptus kraft pulp, dissolving pulp, and microcrystalline cellulose) as reference materials. The nanostructural characteristics were evaluated by calorimetric thermoporometry, X-ray diffraction, and moisture sorption isotherms. Composition was evaluated by standard wet chemical analysis and insights on functional groups were obtained by infrared spectroscopy. The cellulose nanocrystals were produced by acid hydrolysis with sulfuric acid and characterized by atomic force microscopy and X-ray diffraction. The measured parameters of the isolated celluloses were spread, showing we could achieve a highly diverse set of substrates. Significant correlations between measured variables across the sample set, indicating possible unforeseen multivariate relations among cellulose features. For example, we could show that cellulose monolayer hydration is determined by both hemicelluloses content (compositional parameter) as well as cellulose crystal width (structural parameter). Cellulose nanocrystals were successfully produced, although in some cases such as for the acetossolv pulps the acid conditions were too aggressive and oxidized the substrates. Finally, some quantitative correlations were seen between the parameters of cellulose substrates and the resulting cellulose nanocrystals. These results supply the first hints about how the nanostructural variability of isolated cellulose can influence the cellulose nanocrystals produced from them. / Este trabalho investiga a variabilidade composicional e nanoestrutural de celuloses isoladas de plantas e o seu impacto na variabilidade na produção de nanocristais de celulose. Um conjunto variável de celuloses isoladas de plantas foi gerado a partir de uma série de matérias-primas (fibra de coco, sisal, serragem de eucalipto, serragem de pinheiro, casca de cana e miolo de cana), aplicando uma série de processos de isolamento de celulose (hidrotérmico, alcalino, hidrotérmico + alcalino e acetosolve) e adicionando celuloses comerciais (polpa kraft de eucalipto, polpa para dissolução e celulose microcristalina) como materiais de referência. As características nanoestruturais foram avaliadas por termoporometria calorimétrica, difração de raios X e isotermas de sorção de umidade. A composição foi avaliada por análise química húmida padrão e os conhecimentos sobre grupos funcionais foram obtidos por espectroscopia de infravermelhos. Os nanocristais de celulose foram produzidos por hidrólise ácida com ácido sulfúrico e caracterizados por microscopia de força atômica e difração de raios-X. Os parâmetros medidos das celuloses isoladas foram distribuídos, demonstrando que poderíamos alcançar um conjunto altamente diversificado de substratos. Correlações significativas entre as variáveis medidas foram observadas em todo o conjunto amostral, indicando possíveis relações multivariadas imprevistas entre as características da celulose. Por exemplo, poderíamos demonstrar que a monocamada de hidratação de celulose é determinada tanto pelo conteúdo de hemiceluloses (parâmetro de composição) quanto pela largura do cristal de celulose (parâmetro estrutural). Os nanocristais de celulose foram produzidos com sucesso, embora em alguns casos, como nas polpas acetosolve, as condições ácidas fossem muito agressivas e oxidassem os substratos. Finalmente, algumas correlações quantitativas foram observadas entre os parâmetros dos substratos de celulose e os nanocristais de celulose resultantes. Estes resultados fornecem as primeiras dicas sobre como a variabilidade nanoestrutural da celulose isolada pode influenciar os nanocristais de celulose produzidos a partir deles.

Made available in DSpace on 2017-07-10T17:37:11Z (GMT). No. of bitstreams: 1 Jessica Cristina Urbanski Laureth.pdf: 1753789 bytes, checksum: 5516d92f3757c43a94720173f562bc89 (MD5) Previous issue date: 2016-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Edible coatings may assist improvement of quality and conservation of fruits. Polysaccharide polymers, such as starch, pectin and cellulose have been constantly used as base to form coatings, but their physical properties do not provide proper barrier to gas and water vapor diffusion. Cellulose nanocrystals, when incorporated to edible coatings may improve their barrier properties. The addition of a natural antioxidant to the coating may improve conservation capacity of fruit. Natural antioxidants have relative instability, which may limit its reducing properties. Nevertheless, including nanocrystals may aggregate higher stability to added antioxidant. Thus, the objective of this research was assessing the effect of polymeric coatings, along with cellulose nanocrystals and vegetable extract on the physiology of Persian lime. It consisted of two experiments, the first assessed the effect of pectin (PEC), starch (ST) and cellulose gum (CMC) polymers added to cellulose nanocrystals (CN). The second differed from the first due to the addition of peanut peel extract, chosen because it has higher rates of antioxidant activity by DPPH, ABTS and FRAP methods in comparison with extracts of Persian lime and Rangpur seeds. In both experiments the assessments occurred during nine storage days under 23 °C ± 2 °C. Ethylene, CO2, fresh mass loss, firmness and chlorophyll were assessed. In the second were included DPPH, ABTS and FRAP antioxidant activity analyses, as well as total phenolic composites and ascorbic acid. In the first experiment, coatings formed by CMC, PEC and ST pure polymers with their respective nanocomposites called NCMC, NPEC and NST were efficient to reduce ethylene production until first three storage days. Among tested treatments, NPEC nanocomposite (12.01 mg CO2 kg-1 h-1) was more efficient than PEC (14.93 mg CO2 kg-1 h-1) to inhibit CO2 diffusion. PEC polymer when reinforced by NC (NPEC) was the only coating to reduce fresh mass loss of Persian lime, and it was also more efficient than PEC pure polymer when it comes to retention of chlorophyll. All tested nanocomposites and pure polymers were similarly efficient to keep fruit s firmness. In the second experiment the combination of pectin, cellulose gum, nanocrystals and extract was responsible to present lower ethylene and CO2 production rates. All tested coatings slowed fresh mass and firmness loss of fruits, but pectin and cellulose gum active nanocomposite was the coating able to contribute to the lowest rate of fresh mass loss and to highest rate of fruit s firmness retention, but the addition of extract did not influence these results. The reinforcement with cellulose nanocrystals was able to retain antioxidant activity off added coatings, which consisted of peanut peel extract. This research showed that pectin coatings, based on nanocrystals and the coatings from polymeric combination of pectin and cellulose gum, along with peanut peel extract and nanocrystals, presented better barrier properties against gases and water vapor, based on physiologic and physicochemical indicators / Revestimentos comestíveis podem auxiliar na qualidade e conservação de frutos. Polímeros de polissacarídeos, como amido, pectina e celulose têm sido muito utilizados como base de formação de revestimentos, mas suas propriedades físicas não proporcionam barreira adequada à difusão de gases e vapor d´água. Nanocristais de celulose, quando incorporados a revestimentos comestíveis, podem melhorar suas propriedades de barreira. A adição de um antioxidante natural ao revestimento pode melhorar a capacidade de conservação do fruto. Antioxidantes naturais possuem relativa instabilidade que pode limitar suas propriedades redutoras. No entanto, a inclusão de nanocristais pode agregar maior estabilidade ao antioxidante adicionado. Assim, o objetivo deste trabalho foi avaliar o efeito de revestimentos poliméricos, adicionados com nanocristais de celulose e extrato vegetal na fisiologia e qualidade pós-colheita da lima ácida Tahiti. O trabalho foi dividido em dois experimentos. O primeiro consistiu na avaliação do efeito de polímeros de carboximetilcelulose (CMC), pectina (PEC) e amido (AM), adicionados de nanocristais de celulose (NC). O segundo diferiu do primeiro pela adição de extrato de película de amendoim, escolhido por possuir maiores valores de atividade antioxidante pelos métodos DPPH, ABTS e FRAP em comparação aos extratos de casca de lima ácida Tahiti e semente de limão Cravo. Em ambos experimentos as avaliações ocorreram durante 9 dias de armazenamento a 23 °C ± 2 °C. Etileno, CO2, perda de massa fresca, firmeza e clorofila foram avaliados nos dois experimentos. No segundo foram incluídas as análises de atividade antioxidante pelos métodos DPPH, ABTS e FRAP, compostos fenólicos totais e ácido ascórbico. No primeiro experimento, os revestimentos formados com os polímeros puros CMC, PEC e AM e com os seus respectivos nanocompósitos chamados NCMC, NPEC e NAM foram eficazes em reduzir a produção de etileno até os primeiros três dias de armazenamento. Entre os tratamentos testados, o nanocompósito NPEC (12,01 mg CO2 kg-1 h-1) foi mais eficiente em inibir a difusão de CO2 do que o polímero puro PEC (14,93 mg CO2 kg-1 h-1). O polímero PEC quando reforçado com NC (NPEC) foi o único revestimento que pôde reduzir a perda de peso fresco de lima ácida Tahiti, e também foi mais eficiente na retenção de clorofila do que o polímero puro PEC. Todos os nanocompósitos ou polímeros puros testados foram similarmente eficientes em reter a firmeza dos frutos. No segundo experimento a mistura de pectina e carboximetilcelulose, nanocristais e extrato foi responsável por apresentar as menores taxas de produção de etileno e CO2. Todos os revestimentos testados retardaram as perdas de massa fresca e de firmeza dos frutos, mas o nanocompósito ativo de pectina e carboximetilcelulose foi o revestimento capaz de influenciar a menor perda de massa fresca e reter a maior firmeza, mas a adição de extrato não influenciou esses resultados. O reforço com nanocristais de celulose foi capaz de reter atividade antioxidante dos revestimentos adicionados de extrato de película de amendoim. Este estudo mostrou que revestimentos de pectina, baseados em nanocristais e revestimentos da mistura polimérica de pectina e carboximetilcelulose, adicionais de extrato de película de amendoim e nanocristais, apresentaram melhores propriedades de barreira a gases e ao vapor de água, baseados nos indicadores fisiológicos e físico-químicos

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo a Pesquisa do Estado de Minas Gerais / Tese (Doutorado) / Abstract: Since this thesis presents two independent studies on cellulose nanocrystals (CNCs), the abstract was divided in two sections referring to chapters II and III, respectively. Comprehensive morphological and structural investigation of cellulose I and II nanocrystals prepared by sulfuric acid hydrolysis Cellulose has several polymorphs. These polymorphs differ by crystal packing (i.e. unit cell parameters), polarity of the constituting chains and hydrogen bond patterns established between them. Most of cellulose polymorphs result from chemical treatments of the native polymorph, the so-called cellulose I (Cel-I) (Wada et al., 2008). In Cel-I, the chains are parallel and can be packed into two allomorphs, namely Iα and Iβ. Among the cellulose polymorphs, cellulose II (Cel-II), in which the chains are antiparallel, can be prepared from Cel-I by two distinct processes: Mercerization or Regeneration. Mercerization is an essentially solid-state process during which cellulose fibers are swollen in concentrated alkali media and recrystallized into cellulose II upon washing and drying (removal of the swelling agent). Unlike the mercerization process, in process known as regeneration, cellulose is first dissolved in an appropriated solvent and subsequent reprecipitated by adding a non-solvent, leading the chains to recrystallize into into Cel-II polymorph. The Cel-I to Cel-II transition is irreversible, which suggests that Cel-II is thermodynamically more stable (Habibi et al., 2010). Cell-II is the second most extensively studied polymorph due to its technical relevance. Nevertheless, so far, most of investigations involving Cel-II have focused on fibers and only a few recent studies have been carried out on CNCs. Cel-II nanocrystals have been prepared either by acid hydrolysis of mercerized fibers (Hirota et al., 2012; Kim et al., 2006; Yue et al., 2012), mercerization of Cel-I CNCs (Jin et al., 2016), or after recrystallization of fractions of short cellulose chains in solution (Dhar et al., 2015; Hirota et al., 2012; Hu et al., 2014; Sèbe et al., 2012). However, while these studies have generally combined the data from several imaging, diffraction and spectroscopic techniques, a complete structural picture of the nanocrystals has not been reported so far. In this context, the purpose of the research work presented in chapter II was to produce, characterize and compare CNCs obtained from eucalyptus wood pulp using three different methods: i) classical sulfuric acid hydrolysis (CN-I), ii) acid hydrolysis of cellulose previously mercerized by alkaline treatment (MCN-II), and iii) solubilization of cellulose in sulfuric acid and subsequent recrystallization in water (RCN-II). The morphology, crystal structure, crystallinity index, surface charge and degree of polymerization of these nanocrystals were characterized by complementary techniques, namely elemental analysis, zetametry, viscometry, transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Fourier-transform infrared and solid-state nuclear magnetic resonance spectroscopies (FTIR and NMR, respectively). The three types of prepared CNC exhibit different morphologies and crystalline structures. When the acid hydrolysis conditions are set-up in such a way that the crystalline domains in the initial wood pulp and mercerized cellulose (WP and MWP, respectively) are preserved (60 wt% H2SO4, 45°C, 50 min), the resulting nanocrystals retain the fibrillar nature of the parent fibers (i.e., the chain axis is parallel to the long axis of the acicular particles) and their initial allomorphic type (I for WP and II for the MWP). In both cases, the particles are mostly composed of a few laterally-bound elementary crystallites, in agreement with what was shown for cotton CNCs by Elazzouzi-Hafraoui et al. (2008). The unit nanocrystals in CNCs from mercerized cellulose (MCN-II) are shorter but broader than those prepared from cellulose I fibers (CN-I). If harsher conditions are used (64 wt% H2SO4, 40°C, 20 min), resulting in the depolymerisation and dissolution of native cellulose, the short chains (with degree of polymerization DP ≈ 17) recrystallize into Cel-II ribbons upon regeneration in water at room temperature. In these somewhat tortuous ribbons, the chain axis would lie perpendicular to the long axis of the nanocrystal and parallel to its basal plane. In addition, these nanoribbons are very similar in shape and molecular orientation to mannan II nanocrystals prepared by recrystallization of mannan (Heux et al., 2005), a linear polymer of β-(1,4)-D-mannosyl residues, suggesting that this mode of crystallization may be a feature of short-chain linear β-(1,4)-linked polysaccharides. Although similar ribbons of recrystallized cellulose II have been reported by other authors, to our knowledge, it is the first time that a detailed morphological and structural description is proposed in terms of particle morphology, crystal structure and chain orientation. By comparison with the fibrillar nanocrystals prepared by acid hydrolysis of native or mercerized cellulose fibers, the unique molecular and crystal structure of the nanoribbons imply that a higher number of reducing chain ends are located at the particle surface, which may be important for subsequent chemical modification and specific potential applications such as biosensing and bioimaging agents. Therefore this study offers scope to a better understanding of crystalline structure and morphology of CNC obtained by regeneration process with sulfuric acid. Mechanical properties of natural rubber nanocomposites reinforced with high aspect ratio cellulose nanocrystals isolated from soy hulls At present, the most promising application of CNCs is as reinforcement material in the field of polymer nanocomposites.The incorporation of CNCs in polymer matrices generally leads to polymer-based nanocomposite materials with higher mechanical and barrier properties than the neat polymer or conventional composites. Among various factors that influence the efficiency of the reinforcing effect of CNCs, their intrinsic characteristics, including crystallinity and aspect ratio, play a key role (Dufresne, 2012; Favier et al., 1995; Mariano et al., 2014). It is also well-known that these characteristics depend on the source of the original cellulose, on the extraction method and its conditions (including pretreatment). However, it is widely accepted that the raw starting material is the most important factor (Beck-Candanedo et al., 2005; Dufresne, 2012; Elazzouzi- Hafraoui et al., 2008). The reinforcement capability of CNCs is therefore directly linked to the source of cellulose as well as its biosynthesis. Thus, the optimization of the extraction procedure and further characterization of CNCs from different sources of cellulose are crucial for an efficient exploitation of these sources, allowing the selection of the appropriate source (i.e. with targeted morphology) to suit specific end user applications (Brinchi et al., 2013). Natural rubber (NR) is a perfect polymer matrix to be used as a model system to study the effect of filler reinforcement, owing to its high flexibility and low stiffness. Its properties can be tailored by the addition of reinforcing fillers of various surface chemistries and aggregate size/aspect ratios to suit the targeted application. CNCs extracted from different sources have already been studied as nanoreinforcement in NRbased nanocomposites, including CNCs isolated from capim dourado (Siqueira et al., 2010), rachis of palm date tree (Bendahou et al., 2009), sugarcane bagasse (Pasquini et al., 2010; Bras et al., 2010), sisal (Siqueira et al., 2011), and bamboo (Visakh et al., 2012). So far, little results have been reported in the literature on the isolation of CNCs from soy hulls or their use in nanocomposites (Flauzino Neto et al., 2013, Silvério et al., 2014). In this study, CNCs were isolated from soy hulls by sulfuric acid hydrolysis treatment. The resulting CNCs, referred to as CNCSH in the following, were characterized using transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), wide-angle X-ray scattering (WAXS). These CNCSH were used as a reinforcing phase in a NR matrix to prepare nanocomposite films by casting/evaporation at 1, 2.5 and 5 wt% (dry basis) loading levels. The effect of CNCSH on the structure, as well as thermal and mechanical properties of NR, was investigated by means of scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), tensile tests and thermogravimetric analysis (TGA). For the acid hydrolysis treatment, were chose milder conditions compared to those described in Flauzino Neto et al. (2013) in order to avoid as much as possible the hydrolysis of crystalline cellulose domains. The CNCSH was found to have a type I crystal structure, high crystallinity (crystallinity index ≈ 80%), large specific surface area (estimated to be 747 m2.g-1 from geometrical considerations) and high aspect ratio (around 100). This aspect ratio is the largest ever reported in the literature for a plant cellulose source. Futhermore, from microscopic observations it is clearly seen that CNCSH does not consist of partially hydrolyzed microfibril since it displays the classical rod-like morphology of CNC. Thus, soy hull was found to be an interesting source of raw material for the production of CNC, due to the characteristics of the obtained nanocrystals associated with low lignin content and wide availability of this agro-industrial residue. In the meantime, the reuse of this agro-industrial residue goes towards sustainable development and environment-friendly materials. To tailor the dimensions of CNC and take full advantage of this source, special care needs to be paid to the extraction process and its conditions. A milder acid hydrolysis is preferable to improve the extraction yield, preserve the crystallinity of native cellulose and obtain high aspect ratio CNC. As expected, a high reinforcing effect is observed even at low filler contents when using this nanofiller (CNCSH) to prepare nanocomposites with a natural rubber (NR) matrix by casting/evaporation. For instance, by adding only 2.5 wt% CNC, the storage tensile modulus at 25°C of the nanocomposite was about 21 times higher than that of the unfilled NR matrix. This reinforcing effect was higher than the one observed for CNCs extracted from other sources. It may be assigned not only to the high aspect ratio of these CNCs but also to the stiffness of the percolating nanoparticle network formed within the polymer matrix. Moreover, the sedimentation of CNCs during the film processing by casting/evaporation was found to take place and play a crucial role on the mechanical properties. Thus, both the high aspect ratio of the CNC and sedimentation due to the processing technique are involved in the good mechanical results obtained. Indeed, if sedimentation occurs, then a multilayered film results and the CNC content in the lowest layers is higher than the average CNC content. It means that CNC mechanical percolation can occur in the lowest layers for an average CNC content which is lower than the percolation threshold. Hence, the system can be considered as constituted of parallel layers in the direction of the mechanical solicitation (tensile mode), and the CNC-rich layers can support a higher stress leading to a higher modulus value. Moreover, if high aspect ratio CNC is used, then percolation can occur in the lowest layers for lower average CNC contents. An important contribution of this work is to highlight the importance of the sedimentation of CNC during the evaporation step on the mechanical properties of the nanocomposites which is rarely mentioned in the literature.

Tese (doutorado)—Universidade de Brasília, Faculdade de Tecnologia, Departamento de Engenharia Mecânica, 2016. / Submitted by Fernanda Percia França (fernandafranca@bce.unb.br) on 2016-12-12T18:05:06Z No. of bitstreams: 1 2016_RosineideMirandaLeão.pdf: 15233193 bytes, checksum: 920b649f90a15b2cf1f21ba693f6fa96 (MD5) / Approved for entry into archive by Raquel Viana(raquelviana@bce.unb.br) on 2017-01-10T20:10:51Z (GMT) No. of bitstreams: 1 2016_RosineideMirandaLeão.pdf: 15233193 bytes, checksum: 920b649f90a15b2cf1f21ba693f6fa96 (MD5) / Made available in DSpace on 2017-01-10T20:10:51Z (GMT). No. of bitstreams: 1 2016_RosineideMirandaLeão.pdf: 15233193 bytes, checksum: 920b649f90a15b2cf1f21ba693f6fa96 (MD5) / O setor de cana no Brasil vem crescendo desde o início da década de 2000, obtendo uma produção anual de cerca de 654 milhões de toneladas em 2015, tornando o bagaço um importante resíduo agroindustrial. Esse fato leva a utilização de bagaço como fonte para a obtenção de nanocristais de celulose. Portanto, o presente estudo tem como objetivo obter nanocristais de celulose de forma técnica e ambiental que possam ser utilizados em nanocompósitos. Nanocristais de celulose podem ser extraídos por vários métodos, assim, a Avaliação do Ciclo de Vida (ACV) apresenta-se como a metodologia mais indicada para investigar quais as formas mais viáveis de obtenção. Para isso, o inventário dos sistemas englobou a produção de cana-de-açúcar e dos nanocristais. Insumos, energia e processos auxiliares como transporte e uso de combustível também foram quantificados. A unidade funcional adotada foi de 1 kg de nanocristais de celulose. Inicialmente, foram utilizados doze cenários para extração dos nanocristais de celulose que envolveu condições experimentais da literatura abrangendo pré-tratamento e hidrólise. Essas condições permitiram isolar os nanocristais de celulose, como também a composição química do bagaço e de cada fase de tratamento. Assim, as fibras e os nanocristais de celulose foram caracterizados por um conjunto de técnicas (microscopia eletrônica de varredura MEV; microscopia eletrônica de transmissão MET; microscopia de força atômica MFA; espectroscopia de infravermelho com transformada de Fourier FTIR, difração de Raios-X e análises térmicas). Depois da obtenção dos nanocristais de celulose, nanocompósitos de acrilonitrilabutadieno estireno (ABS) reforçados com 0,5, 1,0 e 1,5% de nanocristais de celulose foram obtidos por extrusão. Além disso, a influência do teor de nanocristais de celulose nos nanocompósitos foi estudada por difração de Raios-X,TGA análise termogravimétrica, DSC calorimetria exploratória diferencial e DMA análise dinâmico-mecânica, ensaios mecânicos, análise estatística, MEV e reologia. Os resultados mostraram que em todos os cenários, na fase de pré-tratamento e na produção dos nanocristais, houve uma grande contribuição para os impactos ambientais devido à quantidade de produtos químicos utilizados e, especialmente, ao consumo elevado de água e energia. A composição química do bagaço em massa foi de 39% de celulose, 21% de lignina e 27% de hemicelulose. Entretanto, a caracterização por MEV mostrou que o tratamento mudou a morfologia das fibras, bem como o aumento da rugosidade da superfície. A caracterização por MET mostrou o cumprimento em torno de 44-300 nm e o diâmetro de 10-30 nm. A caracterização por MFA mostrou a morfológia dos cristalitos e aglomerados de nanocristais. A análise de FTIR identificou claramente nos espectros, picos em 890-1364 cm-1 típico de celulose I. E, finalmente a análise de difração raios-X mostrou aumento da cristalinidade com sucessivos tratamentos, resultando em uma cristalinidade de 67% para os nanocristais. Difração de raios-X mostram diminuição do ângulo para os nanocompósitos, comprovando a dispersão da carga na matriz. As curvas TGA mostraram que a inserção dos nanocristais provocou uma estabilidade térmica intermediária para os nanocompósitos, e as curvas DSC para os nanocompósitos mostraram eventos térmicos semelhantes ao ABS. As curvas DMA mostraram aumento do módulo de armazenamento dos nanocompósitos. A adição dos nanocristais de celulose ao ABS, alterou as propriedades do polímero, comprovado estatisticamente. Assim, dependendo da aplicação, dos nanocompósitos terá um desempenho de maior, tração; flexão; impacto, estabilidade; viscosidade ou em termosambientais. ________________________________________________________________________________________________ ABSTRACT / The sugarcane sector in Brazil has been growing since the beginning of the 2000s, obtaining a annual production of about 654 million tonnes in 2015, making sugarcane an important agricultural residue, may generate many applications. This fact carries the use of exceeding bagasse as a source to obtain cellulose nanocrystals. Therefore, the present study aims to obtain cellulose nanocrystals technical and environmental that can be used in nanocomposites. Nanocrystals cellulose can be extracted by various methods, so the Life Cycle Assessment (LCA) is presented as the most appropriate methodology to investigate what the most viable forms of obtainment. For that, inventory of the systems involved the sugarcane and nanocrystals production. Inputs, energy and auxiliary processes such as transportation and fuel use also were quantified. The functional unit used was 1 kg of cellulose nanocrystals. Initially, were used twelve scenarios for extraction of cellulose nanocrystals that involved experimental conditions of the literature including pre-treatment and hydrolysis. These conditions allowed isolation of cellulose nanocrystals, as well as, the chemical composition of the bagasse and of each treatment phase. The fibers and cellulose nanocrystals were characterized by a range of technical (scanning electron microscopy SEM, transmission electron microscopy TEM, atomic force microscopy AFM; infrared spectroscopy Fourier transform FTIR, X-ray diffraction and thermal analysis). After obtaining of the cellulose nanocrystals, nanocomposites of acrylonitrile butadiene styrene (ABS) reinforced with 0.5, 1.0 and 1.5% cellulose nanocrystals were obtained by extrusion. Furthermore, the influence of cellulose nanocrystals content in the nanocomposites was studied by (X-ray diffraction, TGA-thermogravimetric analysis, DSC-differential scanning calorimetry and DMA-dynamic mechanical analysis), mechanical testing, SEM and rheology. The results showed that in all scenarios in the pre-treatment phase and nanocrystals production was there was a great contribution to that contributed to environmental impacts due amounts chemicals used, and especially the high consumption of water and energy. The chemical composition of the bagasse mass was 39% of cellulose, 21% of hemicellulose and 27% of lignin. However, the SEM characterization showed that the treatment changed the morphology of the fibers, as well as, increased surface roughness. The TEM characterization showed lenght around 44-300 nm and a diameter of 10-30 nm. The AFM characterization showed the morphology of the crystallites and agglomerates. The FTIR spectra analysis clearly identified, band in 890-1364 cm-1 characteristic of cellulose I. And, finally X-ray diffraction analysis showed that the crystallinity increased with successive treatments, resulting in nanocrystals with crystallinity, about 67%. X-rays show decreased angle for nanocomposites, showing the load dispersion in the matrix. The TGA curves showed that the insertion of the nanocrystal caused a intermediate in thermal stability for the nanocomposite, and the DSC curves for nanocomposites showed thermal events similar to the ABS. The DMA curves showed increased storage modulus of the nanocomposites. The addition of the cellulose nanocrystals to ABS occurs alteration in polymer properties, statistically confirmed. Thus, depending on the application, each material will have a performance tensile higher; flexural; impact, stability; viscosity or environmental.

Submitted by Alison Vanceto (alison-vanceto@hotmail.com) on 2016-10-17T10:36:12Z No. of bitstreams: 1 TeseRP.pdf: 5529268 bytes, checksum: 93aced0ddae62347123cf0e035cc0af9 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-21T13:55:45Z (GMT) No. of bitstreams: 1 TeseRP.pdf: 5529268 bytes, checksum: 93aced0ddae62347123cf0e035cc0af9 (MD5) / Approved for entry into archive by Marina Freitas (marinapf@ufscar.br) on 2016-10-21T13:55:52Z (GMT) No. of bitstreams: 1 TeseRP.pdf: 5529268 bytes, checksum: 93aced0ddae62347123cf0e035cc0af9 (MD5) / Made available in DSpace on 2016-10-21T13:55:58Z (GMT). No. of bitstreams: 1 TeseRP.pdf: 5529268 bytes, checksum: 93aced0ddae62347123cf0e035cc0af9 (MD5) Previous issue date: 2014-07-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / In this study the potential of cellulose nanocrystals (CNC) as a reinforcement of a thermoplastic polyurethane partially obtained from renewable sources (Bio-TPU) was investigated. The nanocomposites were obtained in the melt state and from solution casting. The CNC were obtained from acid hydrolysis of eucalyptus kraft pulp. They were freeze dried and used with and without surface treatment. Two types of surface treatment were employed: polymer grafting and oligomers grafting. Only the effectiveness of the second treatment could be confirmed by FTIR. CNC’ structural and geometric characteristics, crystallinity degree and thermal stability were determined by infrared spectroscopy (FTIR), transmission electron microscopy (TEM), wide angle X-ray diffraction (WAXD) and thermogravimetric analysis (TGA), respectively. The concentrations of CNC were varied between 0.1 and 5.0 wt %. The rheological properties of the nanocomposites were evaluated in the steady state and oscillatory measurements in order to evaluate the level of dispersion CNCs in TPU. The nanocomposites obtained by solution casting showed good dispersion. In the melt state, only those obtained with treated CNC showed good dispersion. The deformation and elastic recovery of the nanocomposites tests in the melt state were evaluated through creep and constrained recoil rheological essays. Their morphologies were studied by small angle X-ray scattering (SAXS) and scanning electron microscopy (SEM). It was possible to prove the inclusion of CNC in TPU did not change its conformation. The nanocomposites were also characterized according to their: i) mechanical properties, through tensile tests, ii) thermal properties, by using differential scanning calorimetry (DSC) and TGA, iii) thermo-mechanical properties, evaluated by dynamic mechanical thermal analysis (DMTA) and iv) optical properties, through opacity the nanocomposites with 5.0 wt % of CNC shown better performance and similar results were found from solution casting and melt state processing techniques. / Neste trabalho o potencial de reforço de Nanocristais de Celulose (NCC) em uma matriz de poliuretano termoplástico com matéria prima parcialmente de fonte renovável (Bio-TPU) foi avaliado. Os nanocompósitos foram obtidos no estado fundido e por solução. Os NCC utilizados foram obtidos por hidrólise ácida da polpa Kraft de eucalipto previamente branqueada, e foram utilizados depois de liofilizados e após tratamento superficial. Dois tipos de tratamentos superficiais foram realizados: enxertia de polímeros e enxertia de oligômeros. As características estruturais, geométricas, teor de cristalinidade e estabilidade térmica dos NCC antes e após o tratamento superficial foram determinados por técnicas de espectroscopia de infravermelho (FTIR), microscopia eletrônica de transmissão (MET), difratometria de raio-x de alto ângulo (WAXD) e análise termogravimétrica (TGA), respectivamente. Apenas a enxertia de oligômeros pôde ser comprovada por FTIR. Os Nanocompósitos foram preparados com frações mássicas de NCC variando de 0,1 a 5,0 % (m/m) e foram avaliados quanto às propriedades reológicas em regime permanente e oscilatório para determinar o nível de dispersão dos NCC no TPU. Todos apresentaram boa mistura por solução. No estado fundido apenas os NCC tratados apresentaram boa mistura. A deformação e a recuperação elástica dos nanocompósitos no estado fundido foram analisadas em ensaios reológicos de fluência. A morfologia foi avaliada por espalhamento de raio-x a baixo ângulo (SAXS) e microscopia eletrônica de varredura (MEV), sendo possível verificar que a inclusão de NCC não alterou a conformação do TPU. Os nanocompósitos também foram caracterizados quanto às suas propriedades: i) mecânicas (testes de tração), ii) térmicas ((DSC) e TGA), iii) termomecânicas (análise termo dinâmico mecânica (DMTA)) e iv) óticas. Os nanocompósitos obtidos com 5 % de reforço apresentaram melhor desempenho e comparando-se os resultados dos nanocompósitos obtidos no estado fundido e por solução conclui-se que o desempenho de ambos foi similar.

Orientador: José Antônio Malmonge / Resumo: Compósitos particulados de conectividade 0-3 obtidos a partir de cerâmicas ferroelétricas são objetos de inúmeros estudos científicos. Tal fato decorre da necessidade da indústria eletrônica de materiais com altas constantes dielétricas e densidade de energia, para fabricação de componentes passivos integrados em circuitos impressos e fabricação de dispositivos de armazenamento de energia. Por outro lado, a constante dielétrica dessa combinação se limita a baixos níveis para algumas aplicações. A fabricação de compósitos trifásicos vem ganhando atenção devido às elevadas constantes dielétricas obtidas com a inserção de uma terceira fase condutiva. A literatura apresenta tais compósitos com um perfil bem comportado baseado na regra das misturas e na teoria da percolação. Por outro lado, em alguns casos as interações das fases de preenchimento com a matriz, bem como a possível geração de cargas durante o processo de fabricação impedem um comportamento previsível considerando a distribuição não aleatória das fases. Este trabalho teve como objetivo a obtenção e caracterização de compósitos trifásicos empregando-se como matriz o poliuretano a base de água, como segunda fase Titanato Zirconato de Chumbo (PZT) e como terceira fase, para efeito de comparativo, negro de fumo (NF) ou nanocristais de celulose (CNC). Os compósitos trifásicos foram preparados a partir da mistura dos componentes em solução aquosa de PU, e suas propriedades comparadas àquelas obtidas para compósitos bifásic... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Particulate polymeric composite with connectivity 0-3 obtained using ferroelectric ceramics as a filler are objects of numerous scientific studies. This is due to the need of the electronics industry materials with high dielectric constants and high energy density, for the manufacture of integrated passive components in printed circuits and manufacturing energy storage devices. On the other hand, the dielectric constant of this combination is limited to low levels for some applications. The manufacture of three-phase composite has gained attention due to the high dielectric constant obtained by inserting a third conductive phase. The literature shows such composites with a well behaved profile based on the rule of mixtures and percolation theory. Moreover, in some cases the interactions of the filling phase with the matrix, as well as the possible generation of charges during the manufacturing process prevents a predictable behavior considering the non-random distribution of phases. This study aimed to obtain and characterize three-phase composites employing as matrix water-based polyurethane, and as a second phase Lead titanate zirconate (PZT) and as a third phase, for comparative purposes, carbon black (NF) or cellulose nanocrystals (CNC). The three-phase composites were prepared adding the fillers in aqueous PU, and their properties compared with those obtained for biphasic composites PU_PZT, PU_NF and PU_CNC. The characterizations were performed by Scanning Electron Micro... (Complete abstract click electronic access below) / Doutor

CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior / Atualmente à crescente o nÃmero de pesquisas sobre materiais biodegradÃveis e aproveitamento de resÃduos, devido à necessidade de preservaÃÃo dos recursos naturais e outras questÃes ligadas à sustentabilidade. O objetivo do trabalho foi desenvolver filmes biodegradÃveis a partir de gelatina obtida de resÃduos de tilÃpia adicionados de nanocristais de celulose (NC). A formulaÃÃo do filme foi feita com 9,6% de gelatina de peixe e 25% de glicerol (em base seca) variando a quantidade de nanocristais de celulose de lÃnter nas concentraÃÃes de 0, 5, 10 e 15% (em base seca) com uso ou nÃo de ultrassom (US) na preparaÃÃo do filme. A gelatina foi obtida de resÃduos de carne mecanicamente separada (CMS) de tilÃpia. Os filmes foram obtidos por casting e caracterizados quanto à permeabilidade a vapor de Ãgua, propriedades mecÃnicas de resistÃncia à traÃÃo, elongaÃÃo e mÃdulo elÃstico, propriedades tÃrmicas (DSC), Ãpticas, de estabilidade pela cor, morfolÃgicas (MEV) e de hidrofilicidade a partir do Ãngulo de contato. Os filmes obtidos se apresentaram com boa aparÃncia, homogÃneos e manuseÃveis, com boa transparÃncia e com umidade entre 12,5 e 20,7%, diminuÃda significativamente com a adiÃÃo de NC. Os nanocristais de celulose utilizados foram efetivos para reduzir a permeabilidade ao vapor de Ãgua (PVA), a qual foi reduzida significativamente com a utilizaÃÃo de 10% de NC e uso de ultrassom, e com 15% de NC com e sem US. A adiÃÃo de NC incrementou a resistÃncia à traÃÃo e mÃdulo a partir de 5% com um pequeno decrÃscimo na concentraÃÃo de 15%, e o aumentando o mÃdulo elÃstico a 15% de NC com ultrassom. NÃo houve efeito significativo com a adiÃÃo de NC e uso de US na elongaÃÃo dos filmes e nem na opacidade. O uso de ultrassom melhorou a barreira ao vapor de Ãgua, mÃdulo elÃstico e nÃo influenciou significativamente as propriedades de traÃÃo, elongaÃÃo e opacidade. As imagens obtidas por microscopia eletrÃnica de varredura apresentaram aglomerados, possivelmente pela presenÃa de minerais ou estruturas cristalinas de colÃgeno residuais do processo de hidrÃlise para obtenÃÃo da gelatina ou dos filmes, alÃm de processos com o tempo de armazenamento. As anÃlises de DSC mostraram possÃveis fenÃmenos de fusÃo da gelatina e outros processos tÃrmicos simultÃneos no primeiro ciclo, alÃm de processos tÃrmicos no segundo ciclo que podem estar associados à transiÃÃo vÃtrea, os quais nÃo foram influenciados expressivamente pelo teor de NC e pelo uso de US, porÃm foram bastante influenciados pelo tempo de armazenamento dos filmes. Estes apresentaram pequena intensidade de cor que foi mais intensificada com a quantidade de nanocelulose e nÃo variou de forma expressiva com o tempo, indicando que os filmes apresentaram cor estÃvel. O Ãngulo de contato revelou que a NC nÃo interferiu na hidrofilicidade dos filmes. O melhor filme obtido para aplicaÃÃo em alimentos foi o com 10% de nanocelulose e utilizaÃÃo de ultrassom por apresentar melhor barreira à Ãgua e melhores propriedades mecÃnicas, nÃo interferindo na transparÃncia dos filmes. / Currently the studies about biodegradable materials and waste recovery are increasing, due to need to preserve natural resources and other issues related to sustainability. The objective of this work is to develop biodegradable films from tilapia waste gelatin and cellulose nanocrystals (CN). The formulation of the film was made with 9.6% fish gelatin, glycerol 25% (on dry basis) and varying the amount of nanocrystals from linter pulp at concentrations of 0, 5, 10 and 15% (on a dry basis) and the use of ultrasonic treatment (US) in the preparation of films. The films were obtained by casting and characterized with respect to water vapor permeability (WVP), mechanical properties (tensile strength, elongation and elastic modulus), thermal properties (DSC), optical properties, color stability, morphology (SEM) and hydrophilicity by contact angle. The obtained films are presented in good shape, homogeneous and manageable, with good transparency and moisture content between 12.5 and 20.7%, which decreased significantly with adding CN. Cellulose nanocrystals were effective in reducing the permeability, substantially decreasing WVP with use of 10% CN and US, and 15% of NC with US and without US. The addition of CN increased tensile strength from 5% CN and with a small decrease in concentration of 15%. The elastic modulus increased at 15% with US. There was no significant effect with the addition of NC and use of US at elongation of films and no effects in opacity of films. The use of ultrasound has improved barrier to water vapor and elastic modulus, and it did not has significant influence on the properties of tensile strength, elongation and opacity. The images obtained by scanning electron microscopy showed structures originating from gelatin, possibly by presence of minerals or crystal structures of collagen in the process of obtaining gelatin or films, and processes with storage time. The DSC analysis showed possible phenomena of gelatin melting or other thermal processes simultaneously in the first cycle, and thermal processes in the second cycle, which can be associated with glass transition of gelatin. These events were not influenced significantly by CN content and use of US, but were heavily influenced by storage time of films. These showed little color intensity, which was further enhanced by the amount of CN and did not vary significantly with time, indicating that colors of the films were stable. Contact angle analysis have shown that CN did not decrease the hidrofilicity of films. The best film obtained for application to food products was 10% with NC and use of ultrasound due to better barrier to water, improved mechanical properties and the same transparency.

Orientador: Maria do Carmo Gonçalves / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T19:32:01Z (GMT). No. of bitstreams: 1 Brandao_LarissaReis_D.pdf: 4901816 bytes, checksum: e2662ff13e1db4f6ba5a090882ebef83 (MD5) Previous issue date: 2013 / Resumo: Neste trabalho foram preparados compósitos de acetato de celulose e polissiloxano, usando 3-isocianatopropiltrietoxissilano como agente de acoplamento em dois solventes distintos: tetrahidrofurano e N,N-dimetilformamida. A estrutura, os comportamentos térmico e dinâmico-mecânico, e a morfologia dos compósitos obtidos foram investigados. Inicialmente, o acetato de celulose foi modificado com o agente de acoplamento, por meio da reação entre os grupos hidroxila presentes na cadeia do acetato de celulose e os grupos isocianato presentes no agente de acoplamento. Os compósitos de acetato de celulose/polissiloxano foram então preparados usando duas etapas: (1) hidrólise seguida pela reação de condensação do acetato de celulose modificado na presença de água e (2) reação de condensação do acetato de celulose modificado na presença de polidimetilssiloxano com terminações silanol. Os compósitos, preparados em ambos solventes, apresentaram separação de fases que foi confirmada pela presença de micro e nanodomínios de siloxano dispersos na matriz de acetato de celulose, com boa adesão interfacial entre as fases. Os resultados demonstraram, para os compósitos preparados em tetrahidrofurano, que a incorporação da fase polissiloxano na matriz de acetato de celulose causou uma diminuição na temperatura de transição vítrea, módulo de armazenamento e dureza e um aumento do caráter hidrofóbico da superfície do acetato de celulose. Por outro lado, para os compósitos em N,N-dimetilformamida, a incorporação da fase polissiloxano causou um aumento na temperatura de transição vítrea, módulo de armazenamento e caráter hidrofóbico. Os compósitos apresentaram estabilidade térmica similar ao acetato de celulose puro, para os compósitos preparados em ambos os solventes. Foram preparados também nanocompósitos de acetato de celulose/nanocristais de celulose, pelo método casting, usando 3-isocianatopropiltrietoxissilano como agente de acoplamento. Os nanocristais de celulose foram obtidos a partir da hidrólise ácida com ácido clorídrico de fibras de algodão. Os nanocristais apresentaram formato de agulha. Os nanocompósitos preparados foram avaliados quanto às suas características estruturais, térmicas, dinâmico-mecânicas e morfológicas. Os nanocompósitos de acetato de celulose/nanocristais de celulose apresentaram uma diminuição na Tg e um aumento no módulo de armazenamento e no caráter hidrofóbico da superfície do acetato de celulose. Por outro lado, o nanocompósito de acetato de celulose modificado/nanocristais de celulose apresentou diminuição do caráter hidrofóbico quando comparado com o compósito acetato de celulose/polissilsesquioxano. Não foi observada variação na estabilidade térmica. Análises de microscopia eletrônica confirmaram a boa dispersão dos nanocristais de celulose na matriz de acetato de celulose, o que foi também confirmada pela transparência dos filmes obtidos. A metodologia proposta é, portanto, conveniente para a preparação de compósitos de acetato de celulose/polissiloxano, bem como nanocompósitos contendo nanocristais de celulose, o que permite obter materiais com propriedades úteis / Abstract: In this work, cellulose acetate and polisiloxane composites were prepared from 3-isocianatepropiltrietoxisilane as a coupling agent in two different solvents: tetrahidrofurane and N,N-dimethilformamide. The structure, thermal and dynamic-mechanical behavior, and morphology of the obtained composites were investigated. Initially, the cellulose acetate was modified with the coupling agent, by means of a reaction between the hydroxyl groups present in the cellulose acetate chain and the isocianate groups present in the coupling agent. The cellulose acetate/polisiloxane composites were prepared using two steps: (1) hydrolysis followed by condensation reaction of the cellulose acetate modified in the presence of water and (2) condensation reaction of the cellulose acetate modified in the presence of the polidimethilsiloxane with silanol endings. The composites prepared in both solvents presented phase separation which was confirmed by siloxane micro and nanodomains dispersed in the matrix of the cellulose acetate with good interfacial adhesion between the phases. The results demonstrated that for the composites prepared in THF, the incorporation of the polisiloxane phase in the cellulose acetate matrix caused a decreasing in the vitreous transition, storage and hardness moduli and an increasing of the hydrophobic character of the surface of the cellulose acetate. On the other hand, for the composites in DMF, the incorporation of the polisiloxane phase caused an increase in the vitreous transition, storage modulus and hydrophobic character. The composites presented thermal stability similar to the pure cellulose acetate for the composites prepared in both solvents. Nanocomposites of cellulose acetate/cellulose nanocrystals were also prepared of by the casting method using 3-isocianatepropiltrietoxisilane as a coupling agent. The cellulose nanocrystals were obtained from an acidic hydrolysis of cotton fibers. The nanocomposites prepared were investigated according to their structural, thermal, dynamic-mechanical and morphological characteristics. The nanocomposites of cellulose acetate/cellulose nanocrystals presented a decrease in the Tg and an increase in the storage modulus in relation to the CA matrix, but it was not observed a variation in the thermal stability. Microscopic analysis confirmed the good dispersion of the cellulose nanocrystals in the cellulose acetate matrix, which it was also confirmed by the transparency of the obtained films. Therefore, the proposed methodology is convenient for the preparation of the cellulose acetates/polisiloxane as well as nanocomposites containing cellulose nanocrystals, which allows to obtain materials with useful properties / Doutorado / Físico-Química / Doutora em Ciências