This project investigates the moisture barrier properties of bio-based polymers and ways of improving them. The first section addresses the effect of crystallinity on the water permeability of poly(lactic acid) (PLA). The second section investigates PLA/talc composites and PLA/ montmorillonite nanocomposites. The third section is focused on a new polymer, polybutylene succinate (PBS), and its nanocomposites with montmorillonite. In the first section, the water vapour transmission rates (WVTR) through samples of polylactic acid of different crystallinities have been measured. Three different grades of commercial PLA were used with different ratios of L-lactide and D-lactide to give a range of crystallinities from 0 to 50%. Sheets of PLA were prepared by melt compounding followed by compression moulding and annealing at different temperatures and for different times to give the range of crystallinities required. Crystallinity was measured by differential scanning calorimetry (DSC) and the morphology of the samples was observed under crossed polars in a transmitted light microscope. Water vapour transmission rates through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased linearly with increasing crystallinity of the PLA from 0 to 50%. The results are discussed in terms of the effect of crystallinity on solubility and shown to fit the tortuous path model. The model was also successfully used to explain published data on water permeability of polyethylene terephthalate. In the second section, a series of PLA/talc composites and PLA/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The morphologies of the composites were investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was found that the fillers were well dispersed in the polymer matrix. The average aspect ratio of the compounded talc was found to be 8, and that of the nanoclay was found to be 50. Water vapour transmission rates (WVTR) through the films were measured at 38°C and at a relative humidity of 90%. It was found that the measured values of WVTR decreased with increasing filler content and the results gave good agreement with predictions from the Nielsen tortuous path model. In the third section, PBS/ montmorillonite nanocomposites were prepared by melt compounding followed by compression moulding. The melting and crystallisation behaviour of the pure PBS samples were investigated using differential scanning calorimetry (DSC) and cross polarised optical microscopy. A slight decrease of the degree of crystallinity was found in PBS containing 5% nanoclay. The morphology of the composites was investigated using transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) and it was confirmed that that composite structures were intercalated. Water vapour transmission rates (WVTR) through the PBS sheets were measured using a MOCON Permatran-W®398. The measured values of WVTR decreased with increasing nanoclay content. However, the experimental values were all higher than the values predicted by the Nielsen tortuosity model. This result shows that in the case of PBS, which is a highly crystalline polymer, the nanoclay is not as well dispersed and is not as effective in reducing water vapour permeability as in the case of PLA.

Biomass recalcitrance has been recognized as one of the major barriers that hided the cost-effective conversion of lignocellulosic biomass to bioethanol, therefore the current bioconversion process require an essential step known as pretreatment to increase the cellulose accessibility. This thesis provides information about changes in cellulose accessibility upon different pretreatments, along with how these pretreatments alter the chemical and physical structures of biomass, will be extremely helpful to further optimize the current pretreatment process. Multiple promising analytical techniques including Simons’ stain, NMR cryoporometry, relaxometry, mercury porosimetry was introduced and successfully applied on pretreated biomass samples to characterize the cellulose accessible surface area and biomass porosity. Different pretreatments increase cellulose accessibility through different mechanisms to different extent. Dilute acid pretreatment is more effective than steam explosion in terms of increasing accessible surface area of cellulose as reflected by Simons’ stain and NMR cryoporometry, while NMR relaxometry suggested steam explosion is more effective at pore expansion for the cell wall water pools detected by changes in NMR relaxation time. Alkaline pretreatment decreased cellulose degree of polymerization, cellulose crystallinity, lignin content and subsequently increased cellulose accessibility, with sodium hydroxide pretreatment proved to be much more effective compared lime or soaking in ammonia pretreatment. Delignification through alkaline-based pretreatment is found less effective than removal of hemicellulose using acid in terms of cellulose accessibility increase. Lignin didn’t directly dictate cellulose accessibility but rather restricted xylan accessibility which in turn controls the access of cellulase to cellulose. Pore size distribution analysis based on mercury porosimetry also indicated that the most fundamental barrier in terms of biomass porosity scale for efficient enzymatic hydrolysis is the nano-pore space formed between coated microfibrils, despite some of the porous architecture such as cell lumen and pit could be severely destroyed after pretreatment. The action of cellulase on the characteristics of cellulosic fractions obtained from pretreated biomass was also investigated. Cellulose accessibility was found to increase at the beginning of hydrolysis, and after reaching a maximum value then starting to decrease. Enzymatic hydrolysis resulted in a rapid decrease in the cellulose degree of polymerization then gradually leveled off, suggesting the existence of a synergistic action of endo- and exo-glucanases that contribute to the occurrence of a peeling off type mechanism.

Plant cell walls are complex structures that must not only constrain cellular turgor pressure but also allow for structural modification during the dynamic processes of cell division and anisotropic expansion. Cell walls are composed of highly glycosylated proteins and polysaccharides, including pectin, hemicellulose and cellulose. The primary cell wall polysaccharide is cellulose, a polymer composed of high molecular weight !- 1,4-glucan chains. Although cellulose is the most abundant biopolymer on Earth, there is still a lot to learn about its biosynthesis and regulation. This research began by applying a variety of analytical techniques in an attempt to understand differences in cell wall composition and cellulose structure within the plant body, between different plant species and as a result of acclimation by the plant to different environmental conditions. Next, a number of different Arabidopsis thaliana lines possessing mutations affecting cell wall biosynthesis were analyzed for changes in cellulose structure (crystallinity) and biomass saccharification efficiency. One of these mutants, isoxaben resistance1-2 (ixr1- 2), which contains a point mutation in the C-terminal transmembrane region (TMR) of cellulose synthase 3 (CESA3), exhibited a 34% lower biomass crystallinity index and a 151% improvement in saccharification efficiency relative to that of wild-type. The culmination of this research began with a chemical screen that identified the molecule quinoxyphen as a primary cell wall cellulose biosynthesis inhibitor. By forward genetics, a semi-dominant mutant showing strong resistance to quinoxyphen named aegeus was identified in A. thaliana and the resistance locus mapped to a point mutation in the TMR of CESA1. cesa1aegeus occurs in a similar location to that of cesa3ixr1-2, illustrating both subunit specificity and commonality of resistance locus. These drug resistant CESA TMR mutants are dwarfed and have aberrant cellulose deposition. High-resolution synchrotron X-ray diffraction and 13C solid-state nuclear magnetic resonance spectroscopy analysis of cellulose produced from cesa1aegeus, cesa3ixr1-2 and the double mutant shows a reduction in cellulose microfibril width and an increase in mobility of the interior glucan chains of the cellulose microfibril relative to wild-type. These data demonstrate the importance of the TMR region of CESA1 and CESA3 for the arrangement of glucan chains into a crystalline cellulose microfibril in primary cell walls.

O amido é um ingrediente com grande versatilidade de aplicação, e as sementes de jaca, fruto bem difundido, porém pouco aproveitado no Brasil, contêm uma quantidade considerável de amido, sendo ainda fonte de ferro e proteínas. Dessa maneira, os objetivos desse projeto foram a obtenção da farinha de sementes de jaca das variedades mole e dura, a extração do amido utilizando diferentes solventes, e a caracterização de suas propriedades físico-químicas, estruturais e funcionais, bem como a caracterização reológica de dispersões/géis de amido em cisalhamento estacionário e oscilatório. A extração alcalina do amido, além de reduzir significativamente o conteúdo de lipídeos e proteínas, deixando o amido mais puro, promoveu um aumento no teor de amilose e influenciou diretamente as características de inchamento e solubilidade, que apresentaram aumento significativo a partir da temperatura de 70 °C. O aumento da temperatura ocasionou aumento no poder de inchamento e solubilidade, que foi mais pronunciado para a variedade dura, porém esses valores ainda foram considerados baixos (< 17%). Os amidos de sementes de jaca apresentaram grânulos lisos, arredondados e em forma de sino, com formato mais truncado para o amido extraído com hidróxido de sódio. O diâmetro médio dos grânulos de amido foi menor para a extração alcalina, mas sempre com comportamento monomodal. Foi observado um padrão de difração de Raios-X do tipo A para todas as amostras estudadas, e o índice de cristalinidade foi maior para os amidos de sementes de jaca dura, com uma redução estimada em 70% para os amidos obtidos por extração alcalina. A temperatura de gelatinização dos amidos de semente de jaca foi considerada alta (70-100 °C). Os amidos de sementes de jaca dura obtidos na extração com água apresentaram maiores valores de viscosidade de pico e de Breakdown, que representa menor resistência mecânica. A extração com solução de NaOH 0,1 M aumentou a tendência a retrogradação de ~36% (extração aquosa) para 64% e 45% dos amidos de sementes de jaca das variedades mole e dura, respectivamente. Todas as amostras apresentaram comportamento pseudoplástico (n < 1) nas concentrações e temperaturas estudadas, e as dispersões e/ou géis de amido obtidos pela extração alcalina com NaOH apresentaram menor tixotropia e maiores valores de viscosidade. Os modelos Lei da Potência e Herschel Bulkley apresentaram ótimos ajustes aos pontos experimentais (R² ~0,998) para as amostras com 2 e 6 % de amido, respectivamente, porém para a concentração de 5%, o melhor modelo foi função da variedade do fruto usado na obtenção do amido. A dependência das propriedades reológicas com a temperatura foi analisada pela equação de Arrhenius e a energia de ativação foi baixa (15-25 kJ/mol). Quanto ao comportamento viscoelástico, as amostras com 5 e 6% de amido apresentaram comportamento de gel fraco e o aumento da concentração desse polissacarídeo produziu um aumento na elasticidade do material. Os módulos de armazenamento (G\') associados à elasticidade do gel de amido aumentaram durante o seu resfriamento nos ensaios de varredura de temperatura, o que pode ser relacionado à recristalização da amilose durante esse processo e mantiveram-se praticamente constantes no aquecimento isotérmico a 80 °C, sugerindo boa estabilidade térmica do gel. A farinha isolada da semente de jaca pode ser considerada fonte de fibras e apresentou elevados teores de proteínas (~14-16%) e ferro (~85-150 mg/kg). A distribuição do tamanho de partículas da farinha apresentou comportamento bimodal, com grânulos arredondados, presença de fibras e uma matriz proteica envolvendo os grânulos de amido. As propriedades de pasta revelaram maior pico de viscosidade para a farinha de semente de jaca mole. As características encontradas sugerem que os amidos de semente de jaca poderiam ser aplicados na produção de filmes biodegradáveis, e a farinha da semente de jaca poderia ser utilizada em substituição parcial à farinha convencional na fabricação de bolos e biscoitos. / Starch is an ingredient with great versatility of application, and the seeds of jackfruit, a well spread fruit but little exploited in Brazil, contain a considerable amount of starch, being a source of iron and proteins. Thus, the aimes of this project were to obtain the jackfruit seed flour of hard and soft varieties, extraction of starch using different solvents and characterization of its physicochemical, structural and functional properties, as the rheological characterization of dispersion/gels starch under steady and oscillatory shear. Alkaline extraction of starch significantly reduced the content of lipids and proteins, leaving to a purest starch, and promoted an increase in amylose content, besides, directly influenced the swelling and solubility characteristics, which showed a significant increase from the temperature of 70 ° C. The increase in temperature caused an increase in the power of swelling and solubility, which was more pronounced for the hard variety, but these values are still considered low (<17%). Jackfruit seeds starch granules showed smooth, rounded, bell-shaped, and they had more truncated form when starch was extracted with sodium hydroxide. The average diameter of the starch granules was lower for alkaline extraction, but always with monomodal behavior. It was observed diffraction pattern of X-rays of type A for all samples, and the crystallinity index was higher for the starches of hard jackfruit seeds with an estimated reduction of 70% to starches obtained by alkaline extraction. The gelatinization temperature of starches jackfruit seed was considered high (70-100 °C). The hard jackfruit seed starches obtained in the aqueous extraction had higher peak viscosities and Breakdown, what means lower mechanical strength. Extraction with 0.1 M NaOH solution increased the retrogradation of ~ 36% (aqueous extraction) to 64% and 45% of jackfruit seed starch varieties of soft and hard, respectively. All samples exhibited pseudoplastic behavior (n <1) at the concentrations and temperatures studied, and starch dispersions and /or gels obtained by alkaline extraction with NaOH showed lower thixotropy and higher viscosities. Power Law and Herschel Bulkley models showed great adjustments to the experimental points (R² ~ 0.998) for samples with 2 and 6% starch, respectively, but for the concentration of 5%, the best model was a function of the fruit variety used on starch extraction. The dependence of the rheological properties with temperature was examined by the Arrhenius equation and activation energy was low (15-25 kJ / mol). In concern to the viscoelastic behavior, samples of 5 and 6% of starch showed a behavior of weak gel and the increase in concentration of this polysaccharide produced an increase in the elasticity of the material. The storage modulus (G \') associated with the elasticity of the starch gel increased during its cooling in the temperature sweep tests, which may be related to the recrystallization of amylose during this process and remained practically constant in the isothermal heating at 80 °C, suggesting good thermal stability of the gel. The isolated jackfruit seed flour may be considered source of fiber and showed high levels of proteins (~ 14-16%) and iron (~ 85-150 mg / kg). Particle size distribution of the flour showed bimodal behavior with rounded beads, fibers and the presence of a protein matrix surrounding the starch granules. Pasting properties revealed higher peak viscosity for the soft jackfruit seeds flour. The characteristics found suggest that jackfruit seed starch could be applied in the production of biodegradable films, and jackfruit seed flour could be used in partial replacement of conventional flour in the manufacture of cakes and cookies.

Nos últimos anos, pesquisas sobre a produção de nanocristais de amido (NCA) receberam interesse crescente devido a suas diversas aplicações, principalmente como material de reforço de matrizes poliméricas. Nesse contexto, o amido de quinoa (AQ) apresenta características desejáveis na produção de NCA tais como tamanho de grânulo pequeno e conteúdo de amilose relativamente baixo. Assim, o objetivo desta pesquisa foi produzir NCA de quinoa (NCAQ) por hidrólise ácida em diferentes temperaturas (30, 35 e 40) °C. Além disso, foi estudado o efeito da adição dos NCAQ nas propriedades estruturais e físicas de filmes de amido de mandioca. O AQ apresentou diferentes percentagens de hidrólise, no quinto dia, 63%, 73% e 91% para (30, 35 e 40) °C, respectivamente. O AQ (k = 0,59 dias-1) foi hidrolisado mais rápido que o amido de milho ceroso (k = 0,39 dias-1) a 40 °C. O rendimento dos NCAQ diminuiu com o incremento da temperatura de 30 a 40 °C; enquanto que a cristalinidade relativa dos NCAQ não foi alterada (~35%). A morfologia dos NCAQ produzidos a 30 °C foi irregular com tamanho micrométrico, enquanto que os produzidos a 35 e 40 °C apresentaram forma de paralelepípedo com tamanhos entre (50 e 100) nm e (400 e 900) nm (agregados). O diâmetro hidrodinâmico e as propriedades térmicas dos NCAQ diminuíram com o aumento da temperatura da hidrólise; enquanto que a intensidade das bandas FTIR e o potencial zeta aumentaram. As propriedades indicaram que NCAQ foram produzidos somente a (35 e 40) °C com rendimentos de 22,7% e 6,8%, respectivamente. Dessa forma, considerando o rendimento e a temperatura de transição, os NCAQ produzidos a 35 °C foram selecionados para aplicação em filmes de amido de mandioca. Os filmes foram preparados pela técnica do casting, com 4 g de amido de mandioca/100 g de dispersão filmogênica; 25 g glicerol/ 100 g de amido; e 0; 2,5; 5,0 e 7,5 g de NCAQ/ 100 g de amido. Os difratogramas de raios X confirmaram a presença dos NCAQ nos filmes. A adição de NCAQ nos filmes aumentou a rugosidade e o ângulo de contato em concentrações de 5% e 7,5%, a resistência à tração e o módulo elástico, os parâmetros de cor L* e a* em concentrações 7,5%, e a opacidade; enquanto que diminuiu a deformação na ruptura, a permeabilidade ao vapor de água na concentração de 5%, e o brilho. Outras propriedades dos filmes como espessura, umidade, solubilidade, propriedades térmicas não foram alteradas pela adição de NCAQ. Os resultados indicaram que os NCAQ produzidos a 35 °C podem ser usados como reforço em filmes nanocompósitos para melhorar suas propriedades mecânicas. / Recently researches on starch nanocrystals (SNC) production have become of interest due to their many applications, especially as reinforcement in polymeric matrices. Quinoa starch (QS) has desirable characteristics for SNC production such as small granule size and relatively low amylose content. Thus, the objective of this research was to produce quinoa SNC (QSNC) by acid hydrolysis at different temperatures (30, 35 and 40) °C. Furthermore, the effect of QSNC addition on the structural and physical properties of cassava starch films was studied. QS presented different percentages of hydrolysis on the fifth day, 63%, 73% and 91% for (30, 35 and 40) °C, respectively. QS (0.59 days-1) was hydrolyzed more rapidly than waxy maize starch (0.39 days-1) at 40 °C. QSNC yields decreased with temperature increase from (30 to 40) °C, while the relative crystallinity was not altered (~35%). The morphology of QSNC produced at 30 °C was irregular with micrometric size while those produced at 35 °C and 40 °C presented parallelepiped shapes with sizes between 50 nm and 100 nm and 400 nm to 900 nm (aggregates). The hydrodynamic diameter and the thermal properties of QSNC decreased with temperature increase, while the FTIR band intensities and the zeta potential increased. The properties indicated that quinoa QSNC were only obtained at (35 and 40) °C with yields of 22.8% and 6.8%, respectively. QSNC produced at 40 °C presented lower yield and crystallinity than waxy maize SNC, but a lower hydrodynamic diameter. Thus, based on the yield and transition temperature, QSNC produced at 35 °C was selected for application in cassava starch films. The films were prepared by casting technique, with 4 g of cassava starch / 100 g of film forming dispersion; 25 g glycerol / 100 g starch; and 0; 2.5; 5.0 and 7.5 g of QSNC / 100 g of starch. X-ray diffractograms confirmed the presence of QSNC in the films. Addition of QSNC to films increased the roughness and the contact angle at 5.0% and 7.5% concentrations, the tensile strength and elastic modulus, the color parameters L* and a* at 7.5% concentration, and the opacity; while decreasing deformation at break, water vapor permeability at 5.0% concentration, and gloss. Other film properties such as thickness, moisture content, solubility, thermal properties were not affected by QSNC addition. The results indicated that the QSNC produced at 35 ° C can be used as reinforcement in nanocomposite films to improve their mechanical properties.

O desenvolvimento de materiais biodegradáveis, a partir de biopolímeros, para embalagens ou coberturas tem grande interesse para a indústria de alimentos. Na elaboração desses materiais, os amidos e as proteínas são muito usados por serem abundantes na natureza, de baixo custo e apresentam propriedades de formar filmes. A cañihua (Chenopodium pallidicaule), grão alto-andino pouco explorado industrialmente, tem altos conteúdos de carboidratos (~58 %) e proteínas (~18 %), e apresenta potencial para ser utilizado como matéria-prima na extração de amido comercial. Diante desse contexto, o objetivo desse trabalho foi extrair e caracterizar o amido de duas variedades de cañihua, Cupi (CC) e Illpa (CI), e selecionar uma dessas variedades para o desenvolvimento de filmes a base de amido ou de farinha. Além disso, a variedade selecionada foi usada para obter um material rico em amido e proteínas, denominado de farinha, que também foi usado para a produção de filmes biodegradáveis. Os grãos de cañihua das variedades Illpa e Cupi são muito similares na forma e tamanho dos grãos, porém os conteúdos de lipídios e cinzas são maiores para CC e o teor de fibras, para a CI. A extração do amido foi feita com solução de hidróxido de sódio (0,25 % m/v) e suas características estruturais, físico-químicas e funcionais foram determinadas. O rendimento desse processo foi de aproximadamente 33 %, e o amido da variedade CC apresentou maiores teores de lipídeos. Os amidos de ambas as variedades, observados em microscópio de varredura eletrônica, apresentaram superfícies granulares lisas e com formatos esféricos de pequeno tamanho (D[3,2] ~ 0,96 µm). A distribuição de tamanho de partícula, o índice de cristalinidade, os espectros de FTIR, poder de inchamento, propriedades óticas e térmicas foram semelhantes, porém o teor de amilose foi maior para a variedade CC. Maiores valores de solubilidade e viscosidade (propriedades de pasta) foram observados para o amido da variedade Cupi e pode estar associado ao maior conteúdo de amilose. O amido da cañihua Cupi foi selecionado para a produção de filmes, por apresentar maiores teores de amilose e de lipídeos. Na obtenção da farinha de CC, usando soluções de NaOH e HCl (0,2 N), o rendimento foi estimado em 56 % (g/100 g de grãos). O teor de proteínas na farinha foi de 79 % (g/100 g sólidos) em relação ao grão. O alto conteúdo de proteínas favoreceu a formação de aglomerados que foram observados nas micrografias da farinha de CC, que apresentou diferenças nas propriedades óticas, de pasta e de solubilidade em relação ao amido da mesma variedade. Os filmes de amido ou farinha foram obtidos pelo método casting com adição de glicerol como plastificante (15 g/100 g de macromoléculas). A caracterização da microestrutura permitiu observar as diferenças físicas entre os filmes de amido ou farinha de cañihua Cupi, assim como as características estruturais foram úteis para explicar o comportamento das outras propriedades. Em umidades relativas altas, os filmes de amido ou farinha CC apresentam o mesmo comportamento de sorção de umidade e permeabilidade ao vapor de água, no entanto, em contato direito com a água (solubilidade e ângulo de contato), esses materiais apresentaram comportamento diferentes, sendo que os filmes de amido são mais resistentes. As diferenças nas propriedades mecânicas dos filmes de amido e farinha foram significativas (p>0,05). O coeficiente de permeabilidade ao oxigênio foi menor para os filmes de amido do que para a farinha de CC. / The development of biodegradable materials based on biopolymers, films or coatings, have great interest for the food industry. For the production of these materials, starches and proteins are widely used because they are abundant in nature, have low cost and have films-forming property. Cañihua (Chenopodium pallidicaule), high Andean region grain underexplored industrially, has high carbohydrate content (~ 58 %) and proteins (~ 18 %) contents, and has the potential to be used as raw material in commercial starch extraction. In this context, the objectives of this study were to extract and characterize starch from two varieties cañihua, Cupi (CC) and Illpa (CI) and select a variety to develop starch films. Furthermore, the selected variety was used to obtain a rich starch and protein material, known as flour, which was also used to produce biodegradable films. Cañihua grains Illpa and Cupi varieties are very similar in shape and size, but the content of fat and ash are higher for CC and fiber content for the CI. The extraction of starch was performed with sodium hydroxide solution (0.25 % w/v) and their structural, physicochemical and functional characteristics were determined. The yield of this process was approximately 33 %, and CC variety starch showed higher levels of lipids. Starches from both varieties observed in scanning electron microscope, showed smooth granular surfaces and spherical shapes of small size (D3,2 ~ 0.96 µM). The particle size distribution, crystallinity index, FTIR spectra, swelling power, thermal and optical properties were similar, but the amylose content was higher for CC variety. Higher values of solubility and viscosity of pasting properties were observed for CC variety starch and may be associated with higher amylose contents. Cañihua Cupi starch was selected to produce films, due to the higher amylose and lipid content. CC flour was also extracted with NaOH solution and adjusting the pH to 5.0 with HCl (0.2 N) in the protein precipitation step, the yield of this extraction process was estimated at 56 %. The protein content of the flour was 79 % compared to this fraction in the grain. The high protein content favors the agglomerates formation which was observed in the CC flour micrographs that showed differences in solubility, optical and pasting properties. The starch or flour films were obtained by casting method with addition of glycerol (15 g/100 g of macromolecules), as plasticizer. The characterization of the microstructure allowed observation of physical differences between starch or flour films of cañihua Cupi, and also structural characteristics were useful to explain the behavior of the other properties. When submitted to high relative humidity, films exhibited the same moisture sorption capacity behavior and water vapor permeability, however in films were in direct contact to water (solubility analysis and contact angle), the behavior of starch and flour films were different, being the structures of the starch films most resistant. Differences in mechanical properties of starch and flour films were significant (p>0.05). The oxygen permeability coefficient was lower for cañihua Cupi starch films than cañihua Cupi flour films.

Neste trabalho foi estudada a produção, por síntese hidrotermal assistida por microondas, nanoestruturas de pentóxido de nióbio (Nb2O5) a partir do precursor pentacloreto de nióbio (NbCl5). A síntese foi realizada nas temperaturas de 150 e 200 °C durante 130 min, e o produto obtido foi tratado termicamente a temperaturas de 600, 800 e 1000 °C por 60 min com taxa de aquecimento de 10 °C/min. Os produtos obtidos foram caracterizados por análise termogravimétrica (ATG), para detectar a perda de massa com a temperatura; por difração de raios X (DRX), para análise da estrutura cristalina; por espectroscopia de infravermelho por transformada de Fourier (FTIR) e por espectroscopia Raman, para identificação das fases formadas; por microscopia eletrônica de varredura (MEV) e microscopia eletrônica de transmissão (MET), para verificação da morfologia do material; e por espectroscopia de refletância difusa (ERD), para identificar as propriedades ópticas do material. Além dessas, foram realizados cálculos do tamanho do cristalito pela equação de Scherrer. Os resultados indicaram a formação de nanoestruturas com diversas fases cristalinas de nióbio (TT, T, B, M e H-Nb2O5). O tamanho do cristalito variou em função da temperatura de tratamento térmico praticado: entre 35,85 e 38,80 nm para as amostras sintetizadas a 150 °C; e entre 34,84 e 40,93 nm para as amostras sintetizadas a 200 °C. Com a análise por refletância difusa foram obtidos os valores de band gaps para as amostras sintetizadas, e os resultados identificaram material semicondutor com uma variação de 3,13 a 3,90 eV. / In this work was studied the production by hydrothermal synthesis assist for microwave, niobium pentoxide nanocrystals (Nb2O5) obtained from the precursor pentachloride niobium (NbCl5). The synthesis was carried out at temperature of 150 and 200 °C for 130 min and the product obtained was calcined at temperatures 600, 800 and 1000 °C for 60 min and heating rate at 10 °C/min. The following characterizations were performed for analysis of the material, among them, thermal gravimetric analysis (ATG) for detecting the lost mass by temperature, X-ray diffraction (XRD) for analysis of the crystal structure, Fourier Transform Infrared spectroscopic (FTIR) and Raman spectroscopic was used for analyze the changes in superficial chemical connections, scanning electron microscopy (SEM) and transmission electronic microscopic (TEM) for morphology of material and diffuse reflectance spectroscopy (DRS) for identification the material optical properties. Moreover, calculate were realized of crystallite size by Scherrer’s equation. The results showed the formation of nanostrutured with various phases (TT, T, B, M e H-Nb2O5). The crystallite size varied in function of thermal treatment temperature from 35,85 to 38,80 nm for synthesizes samples in 150 °C and 34,84 to 40,93 nm for synthesizes samples in 200 °C. With the analysis by diffuse reflectance were obtained the band gap values for the synthesized samples and the results identify a semiconductor material with a variation from 3,13 to 3,90 eV.

Malgré les efforts de la communauté scientifique, les cellules solaires multijonctions à base de matériaux amorphes, sont limitées par la dégradation sous lumière des matériaux actifs qu'elles emploient - notamment, le silicium amorphe hydrogéné (a-Si:H) ou le silicium-germanium amorphe (a-SiGe:H). Compte tenu de la facilité avec laquelle les dispositifs multijonctions peuvent être fabriqués dans cette filière couches minces, pour que cette filière reste compétitive sur le marché photovoltaïque, il est nécessaire de déposer des matériaux présentant les meilleures propriétés de transport possible, avec une énergie de gap variable comprise entre celle du silicium microcristallin hydrogéné (µc-Si:H, 1.1 eV) et celle du a-SiH (1.7 eV), et peu sensibles au vieillissement sous lumière. Le but de ces travaux de thèse était de développer une nouvelle classe de matériaux satisfaisant les critères précédemment cités, alliant carbone et silicium. En effet, les alliages silicium-carbone microcristallins hydrogénés (µc-Si1−xCx:H), sont des candidats prometteurs pour la réalisation de cellules photovoltaïques (PV): d'une part, la structure microcristalline devrait les rend moins sensible au vieillissement sous lumière, et d'autre part, il est possible de faire varier l'énergie de gap en modifiant le taux de carbone de l'alliage. Dans cette thèse, nous avons étudié les propriétés structurales et électriques de ces alliages à l'aide de nombreuses techniques de caractérisation complémentaires, et en faisant varier de nombreux paramètres de dépôt afin de déterminer celles permettant d'obtenir les meilleures propriétés possibles. Nous avons montré en particulier que ces alliages sont composés de cristallites de taille sous-micrométrique, enrobé dans une matrice de silicium-carbone amorphe (a-Si1−xCx:H). En plus, ces matériaux sont caractérisés par une croissance colonnaire, typique du µc-Si:H, avec la taille moyen des grains qui est contrôler en prévalence par la puissance RF utilisé pour le dépôt. L'incorporation de carbone, qui ne peut pas se passer dans la phase cristalline, cause la formation d'un tissue amorphe interstitielle qui enrobe les grain et en empêche la croissance. Ainsi, l'analyse de l'ensemble de nos résultats nous a permis de proposer un modèle cohérent de la croissance de ces alliages. Les propriétés électriques de nos matériaux ont été étudiées à l'aide des mesures de courant d'obscurité et de photocourant en régime stationnaire, de spectroscopie par interférométrie laser et de photocourant modulé. Nous avons pu établir une corrélation directe entre les propriétés électriques et les conditions de dépôt, mettant notamment en évidence que la présence des cristallites assure une conductivité plus élevée par rapport à du a-Si1−xCx:H, et que l'incorporation de carbone amène à des énergies de gap plus grandes que celle du µc-Si:H. Nous avons également montré que les meilleurs matériaux étaient obtenus pour des puissances RF faibles, de l'ordre de 113 mW/cm2. Des résultats de caractérisation de cellules photovoltaïques de type p-i-n ou n-i-p réalisées à partir de nos alliages, ont été aussi présentés. Les rendements obtenus restent encore modestes (de l'ordre de 3,5%) mais nous avons mis en évidence qu'il est possible de faire varier la tension de circuit ouvert (Voc) des cellules en changeant le taux de carbone incorporé dans les alliages. Ainsi, un paramètre autre que la dilution de silane lors du dépôt peut être utilisé pour contrôler Voc. Ces dispositifs sont les tout premiers déposés et nécessitent encore des étapes d'optimisation. Néanmoins, l'étude approfondie que nous avons réalisée sur ces alliages nous laisse penser qu'ils ont un potentiel intéressant pour les applications PV. / Despite continuous effort, thin-film silicon multi-junction solar cells are still limited by the light-induced degradation of amorphous materials that they employ − hydrogenated amorphous silicon layers (a-Si:H) or amorphous silicon-germanium (a-SiGe:H) layers. To survive, this technology must fully benefit from the ease with which it allows multi-band gap photovoltaic (PV) devices to be assembled. To this end, materials that are stable under light soaking and have an electronic band gap between that of hydrogenated microcrystalline silicon (µc-Si:H, 1.1 eV) and that of a-Si:H (1.7 eV) are needed. The goal of this PhD thesis was to develop a new class of materials satisfying all these requirements by alloying carbon and silicon. Indeed, hydrogenated microcrystalline silicon-carbon alloys (µc-Si1−xCx:H) are a promising candidate for expanding the toolbox of useful materials for thin-film photovoltaics. The interest in these alloys lies in the possibility of easily varying their effective band gap by changing the amount of carbon in their composition. In this thesis, the usefulness of such materials in thin-film PV devices was probed using a broad range of deposition and characterization techniques. Using thin-film growth techniques at low temperatures (175−300° C), the range in which such electronically useful materials can be grown has been explored. It was confirmed that even in the condition of small crystallites, no stable sub-stoichiometric Si-C crystalline phase exists (i.e. no parallel for silicon-rich c-SiGe has been observed). Under all deposition techniques utilized, these materials were composed of submicron-size silicon crystallites embedded in an amorphous silicon-carbon (a-Si1−xCx:H) matrix. However, while the presence of the crystallites assures a higher conductivity compared to a-Si1−xCx:H, the carbon incorporation leads to an effective energy gap larger than that of microcrystalline silicon, supporting our investigation of these materials as promising optoelectronic layers. In the first part of this work, different Plasma Enhanced Chemical Vapor Deposition strategies have been investigated to achieve the widest range of processing conditions and to learn the most about the growth conditions required to produce a high quality µc-Si1−xCx:H material. Material properties were extensively characterized both on the structural side and also from an electrical point of view, in order to establish a correlation between the deposition parameters and the microstructural, transport and defect-related properties. The extensive set of results has allowed the proposal of a coherent growth model for such µc-Si1−xCx:H thin films. Exploiting these results, PV devices using these alloys as active layers were made. Although the absolute levels of efficiency (around 3.5 %) are not as high as state-of-the-art microcrystalline silicon, this work showed that it is possible to obtain variations in the open circuit voltage by varying the amount of carbon incorporated in such µc-Si1−xCx:H alloys. This important result shows that a process parameter other than silane dilution can be used to control this aspect of device performance. PV performances are modest so far, which is expected as these are the first ever results concerning the application of such a new class of materials as the active layer in thin-film solar cells. However, with further advancements in such materials, their replacement of the less stable a-SiGe:H is not unforeseeable.

The current research is part of a wider experimental program on creep modeling of glass mat reinforced polypropylene composites which are increasingly being used in molding automotive parts. This specific study is focused on the dimensional and thermal stability of chopped fibre mat and long fibre mat composites. The objective of the study is two-fold. First, to characterize in-situ the micro-failure mechanisms associated with damage accumulation during creep at room temperature and at service temperature (80°C) for stresses up to 67% of the ultimate tensile strength. Second, to characterize the effects of prolonged exposure at elevated temperature on the crystallinity and chemical degradation of the polypropylene matrix. In the first part of the investigation, micro-failure mechanisms including fibre-matrix interface, matrix yielding and cracking during the creep process have been captured in-situ using reflection microscopy. Specimens with 12 mm gauge length were mounted onto a Minimat tensile tester. The applied stress levels of interest were 33% and 67% of the ultimate tensile strength (UTS) at room temperature (RT) and high temperature (HT), respectively. It was found that the deformation mechanisms do not change with temperature but creep in the chopped fibre material is substantially higher than that in the long-fibre. Creep deformation is typically associated with multiple transverse crack initiation at the fibre-matrix interface, crack crazing and rapid coalescence of the small cracks leading to abrupt fracture. Debonding of the fibres is usually detected at the loading stage of the test but fibre breakage is minimal even at high temperature. The change in creep strain at room temperature is similar for both composites but creep strains are highly sensitive to the fibre-mat type at higher temperature. Long-fibre mat structures offer greater creep resistance. Micro-indentations on the matrix-rich regions showed elongation along the loading direction but shear yielding (distortion of indentations) was not noticeable. Using scanning electron microscopy (SEM), the fibre pullout was observed to be pronounced thus suggesting poor adhesion at the fibre-matrix interface. In the second part of this study, the effects of elevated temperature aging on the microstructural changes of isotactic polypropylene matrix in a composite have been studied using wide-angle X-ray scattering (WAXS) and Fourier-transform infrared spectroscopy (FTIR). The objective was to quantify small and slow changes in crystallinity due to thermal aging. To minimize sample variability, polypropylene resin was extracted from the molded composite plaque. Changes in crystallinity level and crystalline form were detected using WAXS after prolonged aging at 90 and 140 °C. FTIR was utilized to monitor in-situ crystallinity changes and to detect oxidation products due to thermal decomposition. The level of crystallinity was monitored by changes in the absorbance ratio of A997/A973 and A841/A973; the former ratio was found to be more sensitive for detecting crystallinity changes. Aging at 140°C resulted in oxidation. The kinetics of secondary crystallization for the aging conditions studied was characterized using Avrami plots.

The current research is part of a wider experimental program on creep modeling of glass mat reinforced polypropylene composites which are increasingly being used in molding automotive parts. This specific study is focused on the dimensional and thermal stability of chopped fibre mat and long fibre mat composites. The objective of the study is two-fold. First, to characterize in-situ the micro-failure mechanisms associated with damage accumulation during creep at room temperature and at service temperature (80°C) for stresses up to 67% of the ultimate tensile strength. Second, to characterize the effects of prolonged exposure at elevated temperature on the crystallinity and chemical degradation of the polypropylene matrix. In the first part of the investigation, micro-failure mechanisms including fibre-matrix interface, matrix yielding and cracking during the creep process have been captured in-situ using reflection microscopy. Specimens with 12 mm gauge length were mounted onto a Minimat tensile tester. The applied stress levels of interest were 33% and 67% of the ultimate tensile strength (UTS) at room temperature (RT) and high temperature (HT), respectively. It was found that the deformation mechanisms do not change with temperature but creep in the chopped fibre material is substantially higher than that in the long-fibre. Creep deformation is typically associated with multiple transverse crack initiation at the fibre-matrix interface, crack crazing and rapid coalescence of the small cracks leading to abrupt fracture. Debonding of the fibres is usually detected at the loading stage of the test but fibre breakage is minimal even at high temperature. The change in creep strain at room temperature is similar for both composites but creep strains are highly sensitive to the fibre-mat type at higher temperature. Long-fibre mat structures offer greater creep resistance. Micro-indentations on the matrix-rich regions showed elongation along the loading direction but shear yielding (distortion of indentations) was not noticeable. Using scanning electron microscopy (SEM), the fibre pullout was observed to be pronounced thus suggesting poor adhesion at the fibre-matrix interface. In the second part of this study, the effects of elevated temperature aging on the microstructural changes of isotactic polypropylene matrix in a composite have been studied using wide-angle X-ray scattering (WAXS) and Fourier-transform infrared spectroscopy (FTIR). The objective was to quantify small and slow changes in crystallinity due to thermal aging. To minimize sample variability, polypropylene resin was extracted from the molded composite plaque. Changes in crystallinity level and crystalline form were detected using WAXS after prolonged aging at 90 and 140 °C. FTIR was utilized to monitor in-situ crystallinity changes and to detect oxidation products due to thermal decomposition. The level of crystallinity was monitored by changes in the absorbance ratio of A997/A973 and A841/A973; the former ratio was found to be more sensitive for detecting crystallinity changes. Aging at 140°C resulted in oxidation. The kinetics of secondary crystallization for the aging conditions studied was characterized using Avrami plots.