Do ponto de vista reológico, o concreto fresco flui como um líquido. Sendo assim, o seu comportamento no estado fresco deve ser estudado a partir dos conceitos da reologia, ciência voltada para o estudo das deformações e escoamento de um fluido sob a influência de tensões. As estruturas bem planejadas, dependendo do processo adotado para sua confecção, são executadas em tempo muito pequeno após a mistura dos materiais que irão constituir os concretos. Assim, a trabalhabilidade do concreto é um parâmetro importante a ser estudado, tanto por facilitar o lançamento do material quanto pelas decisões relacionadas com a forma desse lançamento. Tradicionalmente, a trabalhabilidade do concreto está associada à sua consistência, expressa em termos de abatimento obtido no ensaio de tronco de cone, que, apesar de ser um método de ensaio bastante utilizado, não a quantifica totalmente. Isto porque o concreto se comporta como um fluido binghamiano, sendo, então, caracterizado por dois parâmetros reológicos: a tensão de escoamento e a viscosidade plástica. Assim, o presente trabalho determina alguns parâmetros de medida, a partir de conceitos reológicos, para a verificação do comportamento de alguns tipos de concreto de alto desempenho no estado fresco, com adição de sílica ativa. Para isso, foram usados tanto os métodos de ensaios tradicionais - ensaio de abatimento de tronco de cone e consistômetro de Ve-Be - quanto equipamentos mais modernos - reômetro. Uma modificação do ensaio de abatimento tradicional também foi usada como uma tentativa de simplificar a determinação dos parâmetros reológicos que caracterizam o comportamento dos concretos frescos. A capacidade dos concretos escoarem sob influência do seu peso próprio foi avaliada através do ensaio da caixa L. A identificação da natureza reológica dos concretos foi feita com o auxílio de um reômetro. A trabalhabilidade dos concretos foi avaliada a partir dos métodos de ensaio que medem os dois parâmetros reológicos e sua perda ao longo do tempo foi associada à evolução dos parâmetros medidos. Apesar de terem sido classificadas como misturas fluidas, nenhum concreto apresentou escoamento suficiente que o caracterizasse como um material auto-adensável, porém apresentou bom escoamento sob a energia de um vibrador. A natureza reológica dos concretos foi identificada como sendo realmente semelhante a um fluido binghamiano. A trabalhabilidade, bem como sua perda ao longo do tempo, foram associadas à evolução dos parâmetros reológicos: observou-se um aumento da tensão de escoamento (ou torque de escoamento), enquanto a viscosidade plástica (ou viscosidade de torque) permaneceu praticamente constante durante os 60 minutos em que o comportamento foi acompanhado. Conclui-se que para a trabalhabilidade dos CAD, há inúmeros outros fatores importantes a serem considerados no prosseguimento da pesquisa, os quais deverão levar em conta parâmetros associados à produção, ao transporte e ao lançamento do material. / From the rheological point of view, the fresh concrete flows as a liquid. In such case, its fresh behavior should be studied from the concepts of rheology, the science which concerns the study of deformation and flow of a fluid under stress influence. The well designed structures, depending on the process considered in their production, are performed in a very short time after the mixture of the materials that will constitute the concretes. Thus, the concrete workability is an important parameter to be studied, even for facilitating the material placement and for the decisions related with the method of this process. Traditionally, the concrete workability is associated to its consistency, expressed in terms of the slump value measured by the slump test that, in spite of being a quite used test, does not quantify it totally. It happens because the concrete behaves as a Bingham fluid, being described by two rheological parameters: the yield stress and the plastic viscosity. Thus, the present research determines some measure parameters from rheological concepts to verify the behavior of some types of fresh high performance concrete (with silica fume addition). For this, both traditional test methods - slump test and Vebe consistometer - and more recent equipments - rheometer - were used. A modification of the traditional slump test was also used as an attempt to simplify the determination of the rheological parameters that describe the fresh concretes behaviors. The capacity of the concretes flow under the influence of their own weight was evaluated by the L-box test. The identification of the concretes rheological behavior was made with a rheometer. The concretes workability was evaluated from test methods that measure the two rheological parameters and its loss over time was associated to the evolution of the measured parameters. In spite of being classified as fluid mixtures, none of the concretes presented enough flow to describe it as a self-compacting material; however they presented a good flow under vibration energy. The concrete rheological behavior was identified as being similar to a Bingham fluid. The workability, as its loss over time, was associated to the evolution of the rheological parameters: an increase of the yield stress (or flow resistance) was observed, while the plastic viscosity (or torque viscosity) stayed practically constant during the 60 minutes in which the behavior was followed. It is concluded that for the high performance concretes workability, there are other several important factors to be considered in the research pursuit, which should consider the parameters associated to the material\'s production, transport and placement.

Cement has three sequential states in most applications: fluid, setting and hardened. This thesis focuses on the effect of nanoclays and diutan gum on rheological, chemical and mechanical properties corresponding to the three states. Water transport properties are critically important in many applications, such as oil well cementing and 3D concrete printing. The effect of nanoclays and diutan gum on water transport properties of cement pastes were investigated. Bleeding, water retention under suction pressure, and evaporation under air flow were measured. The nanoclay was found to reduce bleeding but had no effect on water retention or evaporation. The diutan gum was found to reduce bleeding, improve water retention, and decrease evaporation loss. The rheological properties of the pastes and their interstitial solution were also characterized to resolve the mechanisms underlying the water transport behaviors. Good correlation between the measured rheological parameters and water transport properties was found. In addition to water retention, the static yield stress build-up plays a major role in the successful oil well cementing and 3D concrete printing. Linear models are commonly used to describe the early structural build-up of cement-based materials. However, some studies have shown that there exists a faster non-linear phase before the linear phase. A simple non-linear thixotropy model is presented to describe the structural build-up process. It was quantified using static yield stress and storage modulus, which are measured through the stress growth protocol and small amplitude oscillatory shear (SAOS) tests, respectively. The effect of pre-shear, rest condition and nanoclay and diutan gum on the build-up behavior are studied. The results showed distinctly different trends between static yield stress and storage modulus. This may be attributed to the two different structures of fresh cement pastes, i.e. floc structures and C-S-H structures, measured by the stress growth protocol and SAOS test, respectively. Phase characterization of cement paste was performed through synchrotron x-ray diffraction technique. This allowed for real-time, in-situ measurements of x-ray diffraction patterns to be obtained, and subsequently the continuous formation and decomposition of select phases over time (up to 8 hours). Phases of interest included alite, ferrite, portlandite, ettringite, monosulfate, and jaffeite (crystalline form of calcium silicate hydrate). The effects of elevated temperatures at elevated pressure, as well as the effect of nanomaterial addition were investigated. Rate of conversion of ettringite to monosulfate increased with increasing temperature, and monosulfate became unstable when temperatures reached 85ºC. The synchrotron x-ray diffraction setup appeared to have captured the seeding effect of nano-sized attapulgite clays at 0.5% addition by mass of cement, where acceleration in the rate of formation of portlandite and jaffeite was observed. Finally, the investigated system was upscaled from cement paste to cement mortar incorporating the fly ash and the slag. The effect of the nanoclays on the mechanical properties was evaluated in comparison with the carbon nanotube. Compressive strength and tensile strength were evaluated. Results indicated that although the nanoclays are utilized primarily as a rheological modifier, they can also enhance mechanical properties.

La rhéologie des fluides complexes est un sujet à l’intérêt grandissant dans le domaine de la recherche appliquée. Toutefois, les rhéomètres classiques nécessitent de grands volumes d'échantillons et sont généralement limités à une plage relativement étroite de fréquences de fonctionnement. En outre, seuls quelques rhéomètres sont dédiés à desmesures à hautes pressions, qui sont pourtant essentielles pour résoudre certains des problèmes rencontrés dans l’industrie pétrolière. Par conséquent, dans le cadre de cette thèse, un rhéomètre piézo-électrique à vibrations axiales est présenté. Il peut produire des données sur une large gamme de fréquences continues (1 Hz à 8 kHz). Il peut êtreutilisé avec de faibles quantités d'échantillons (jusqu'à 10 μL) et a servi pour la caractérisation d’huiles de synthèse. Enfin, cet appareil a été adapté pour faire face à des conditions de haute pression. Pour ce faire, une nouvelle conception de la cellule a été nécessaire et est présentée dans ce travail. Ce projet de thèse permettra d'étudier les propriétés de transport des huiles lourdes et de concilier les données obtenues dans les domaines de la sismique et de la pétro-acoustique. / Rheology of complex fluids is growing topic in applied research. However, the conventional rheometers require large sample volumes and are usually limited to a relatively narrow range of operating frequencies. Furthermore, only few rheometers are dedicated to high pressures conditions, which are nevertheless crucial to tackle some of the petroleum industry problem. Therefore, in this thesis, a piezoelectric axial vibrator rheometer is presented which can produce data for a large continuous frequency range (1 Hz to 8 kHz). It can be used for very small amount of samples (down to 10μL) andhas been employed to characterize synthetic oil. Then, this apparatus has been adapted to deal with High Pressure conditions. To do so, a new design of the cell has been required and is presented in this work. This thesis project will allow studying the transport properties of heavy oils to conciliate the data obtained in the areas of seismic and petro-acoustic.

Introdução: A estabilidade fisica de sistemas emulsionados pode ser avaliada através de avaliação da distribuição de gotículas, propriedades reológicas, termoanálise, microscopia, entre outras técnicas. Objetivo: Avaliar a estabilidade fisica de emulsões obtidas com diferentes concentrações de emulsificantes aniônicos (A - cetil fosfato de potássio 3, 5 e 7%) e não-iônicos (N monoestearato de glicerila, 3, 5 e 7%), e a influência da transposição de escala de produção. Metodologia: Avaliação da distribuição das gotículas formadas através de difração de raio laser, análise reológica do tipo fluxo, microscopia e termogravimetria. Resultados e Conclusão: Os valores de 90% das gotículas foram menores que 92,66 µm; 50,28µm e 38,80µm, respectivamente para 3, 5 e 7% de emulsificante N. No sistema A, 90% das gotículas foram menores que 3,85µm; 4,89µm e 63,57µm, para 3, 5 e 7%, respectivamente. O aumento de escala de produção influenciou ambos os sistemas, com aumento de viscosidade: Sistema A: de 6,614 Pa.s para 81,55 Pa.s e Sistema N - de 3,366 Pa.s para 7,153 Pa.s no sistema N. Na análise TG, somente água livre pôde ser detectada no sistema N e, no sistema A, água interlamelar e livre puderam ser detectadas (inicial e em estabilidade) / lntroduction: The physical stability of emulsions can be evaluated through droplets distribution evaluation, rheological properties, thermal analysis, microscopy and others. Objective: Evaluate the physical stability of emulsions containg different concentrations of anionic (A - potassium cetyl phosphate 3, 5 e 7%) and non-ionic emulsifiers (N - glyceril monostearate, 3, 5 e 7%), and the influence ofthe scale-up processo Methodology: Evaluate the droplets distribution with laser diffraction, rheology analysis, microscopy and thermogravimetry (TG). Results and Conc1usion: The values of 90% of the droplets were below 92.66 µm, 50.28µm and 38.80µm, respectively for 3, 5 and 7% ofN emulsifier. For system A, 90% ofthe droplets were below 3.85µm, 4.89µm and 63.57µm, for 3, 5 and 7%. The scale-up process influenced both systems, with an increase in the viscosity on system A from 6.614 Pa.s to 81.55 Pa.s and from 3.366 Pa.s to 7.153 Pa.s for system N. ln the TG analysis, only bulk water could be detected in system N and, in the system A, both interlamellar and bulk water were detected (initial and stability).

No presente projeto, foi estudada a viabilidade do purê de manga (Mangifera indica Linn.), variedade 'Haden', para pronto consumo. Inicialmente foi feito o acompanhamento do processo de amadurecimento das mangas para determinar o estágio de maturação adequado para o processamento do purê. Foram feitas análises de firmeza, pH, acidez titulável expressa em porcentagem de ácido cítrico, sólidos solúveis e teor de pectina da polpa das frutas. Os resultados mostraram que a coloração da casca foi um bom indicador do estágio de maturação das mangas. Após acidificação, foram alicados no purê quatro tratamento térmicos diferentes: 25,5 minutos a 65°C; 16,0 minutos a 75°C; 4,0 minutos a 80°C e 2,5 minutos a 95°C. Purê tratado e não tratado termicamente foi mantido sob refrigeração durante 36 dias e análises de pH e acidez titulável, além da contagem de bolores e leveduras, foram realizadas no purê na freqüência de 7 dias. Apesar da análise estatística indicar diferenças significativas entre os valores de pH e acidez titulável em função do tempo de armazenamento e do tratamento térmico, o purê apresentou valores dentro dos limites estabelecidos pela legislação para purê de manga destinado ao consumo como bebida (valor de pH entre 3,3 e 4,5 e acidez titulável mínima de 0,32% de ácido cítrico). Em relação à contagem de bolores e leveduras, o purê tratado termicamente mostrou-se estável, apresentado contagem zero dos microrganismos citados durante todo o período de armazenamento. Estudo do comportamento reológico do purê tratado e não tratado termicamente indicou o seu caráter não-newtoniano, de natureza pseudoplástica. Apesar dos tratamentos térmicos apresentarem valores de F bem distintos, as análises físico-químicas, a contagem de bolores e leveduras e o estudo reológico mostraram que não houve diferença entre os produtos finais. Isso indica que a estabilidade físico-química e microbiológica do purê pode ser alcançada com o tratamento térmico que apresentou o menor valor de F, no caso, o tratamento conduzido a 65ºC durante 25,5 minutos. Em um teste de aceitação do consumidor, o purê tratado nestas condições apresentou um alto indice de aceitação, o que reforça a viabilidade do produto pronto para consumo. / In this research project, the viability of 'Haden' mango puree (Mangifera indica Linn.) as a ready-to-serve product was studied. The ripening process of the fruti was studied to determine the adequate stage for the puree production. Firmness, pH, total acidity expressed as citric acid percentage, soluble solids and pectin content of the fruti pulps were analyzed. results showed that color of skin is a good parameter to indicate the mangoes ripening stage. Four different heat treatments were applied to the acidified puree: 25.5 minutes at 65°C; 16.0 minutes at 75°C; 4.0 minutes at 80°C and 2.5 minutes at 95°C. Non treated and treated puree were maintained under refrigeration for 36 days. pH, titrable acidity, molds and yeast analyses were carried out weekly. Although statistical analyses indicate significant difference among pH and acidity values in relation to storage time and heat treatment, the puree presented acceptable values by Brazilian legislation for mango puree consumed as beverage (pH between 3,3 and 4,5 and mininum total acidity of 0,32% of citric acid). Heat treated puree showed microbiological stability, presenting zero count of these microorganisms during the storage time. The study of rheological behavior of treated and non treated purees revealed non Newtonian character of shear thinning nature. Even though the heat treatments presented very distinct F values, the physical chemical analyses, the mold and yeast counts and the rheological behavior showed that there was difference among the final products. This indicates that the stability os the puree can be achieved applying the heat treatment with the smallest F value, that is 25.5 minutes at 65°C. Consumer acceptance test of puree treated in these conditions presented high level of acceptance, which reinforces the viability of this puree as a ready-to-serve product.

Lau Yiu Kee. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references (leaves 142-146). / Abstracts in English and Chinese. / LIST OF TABLES --- p.viii / LIST OF FIGURES --- p.x / Chapter 1. --- INTRODUCTION --- p.1 / Chapter 1.1 --- Motivation --- p.1 / Chapter 1.2 --- Railway Vehicle Suspension --- p.2 / Chapter 1.3 --- Semi-Active Magnetorheological Fluid Damper --- p.3 / Chapter 1.4 --- Research Objectives --- p.4 / Chapter 1.5 --- Thesis Outline --- p.5 / Chapter 2. --- BACKGROUND --- p.7 / Chapter 2.1 --- MR Fluids --- p.7 / Chapter 2.1.1 --- Composition of MR fluids --- p.7 / Chapter 2.1.2 --- Properties and characteristics of MR fluids --- p.8 / Chapter 2.1.3 --- Literature review --- p.13 / Chapter 2.2 --- MR Devices --- p.13 / Chapter 2.2.1 --- Advantages of MR devices --- p.13 / Chapter 2.2.2 --- Common device geometries --- p.14 / Chapter 2.2.3 --- MR fluid based applications --- p.15 / Chapter 2.2.4 --- Literature review --- p.19 / Chapter 2.3 --- Overview of Railway Vehicles --- p.21 / Chapter 2.3.1 --- "Passive, active and semi-active suspensions" --- p.21 / Chapter 2.3.2 --- Basic railway vehicle structure --- p.23 / Chapter 2.3.3 --- Literature review --- p.25 / Chapter 2.4 --- Railway Vehicle Suspension Systems --- p.25 / Chapter 2.4.1 --- Primary vertical suspension --- p.25 / Chapter 2.4.2 --- Secondary vertical suspension --- p.27 / Chapter 2.4.3 --- Secondary lateral suspension --- p.27 / Chapter 2.4.4 --- Yaw suspension --- p.28 / Chapter 3. --- DESIGN CONSIDERATIONS FOR MR DAMPERS --- p.29 / Chapter 3.1 --- Overview of Existing MR Dampers --- p.29 / Chapter 3.1.1 --- Monotube MR fluid damper --- p.29 / Chapter 3.1.2 --- Double-ended MR damper --- p.31 / Chapter 3.1.3 --- Bellow type MR damper --- p.35 / Chapter 3.2 --- Optimal Design and Configuration of Magnetic Circuit --- p.35 / Chapter 3.2.1 --- Magnetic circuit and magnetic field orientation --- p.35 / Chapter 3.2.2 --- Physical dimension of MR damper --- p.38 / Chapter 3.2.3 --- Connection polarity of electromagnetic circuit --- p.40 / Chapter 3.3 --- Basic Geometry Design Considerations --- p.43 / Chapter 3.3.1 --- Controllable force and dynamic range --- p.43 / Chapter 3.3.2 --- Geometry constraints --- p.45 / Chapter 3.3.3 --- Magnetic circuit design --- p.47 / Chapter 4. --- DEVELOPMENT AND FABRICATION OF MR DAMPERS --- p.51 / Chapter 4.1 --- Pneumatic Air Cylinder --- p.51 / Chapter 4.2 --- Fabrication Process of Double-Ended MR Dampers --- p.55 / Chapter 4.2.1 --- Modifications on the pneumatic air cylinder --- p.55 / Chapter 4.2.2 --- Manufacturing processes of the piston sleeve --- p.56 / Chapter 4.2.3 --- Modification processes of the original piston rod --- p.59 / Chapter 4.2.4 --- Modification of the piston staging area --- p.60 / Chapter 4.2.5 --- Copper wire wrapping and damper assembling --- p.63 / Chapter 5. --- EXPERIMENTAL SETUP AND RESULTS --- p.66 / Chapter 5.1 --- Experimental Setup for the Double-Ended MR Damper --- p.66 / Chapter 5.1.1 --- Instron 8801 loading machine --- p.66 / Chapter 5.1.2 --- Experimental setup for testing the MR damper --- p.67 / Chapter 5.2 --- Force-Lag Phenomenon of MR Damper --- p.70 / Chapter 5.2.1 --- Force-lag phenomenon --- p.70 / Chapter 5.2.2 --- Reasons of the force-lag phenomenon --- p.73 / Chapter 5.2.3 --- Methods to eliminate the force-lag phenomenon --- p.76 / Chapter 5.2.4 --- Setup for hydraulic pump system --- p.77 / Chapter 5.2.5 --- Results and effects of the pressurized MR damper --- p.79 / Chapter 5.3 --- Experimental Results for Testing the MR Damper --- p.83 / Chapter 6. --- SIMULATION RESULTS OF SEMI-ACTIVE TRAIN SUSPENSION --- p.87 / Chapter 6.1 --- MR Damper Model --- p.87 / Chapter 6.2 --- Rail Vehicle Model --- p.92 / Chapter 6.3 --- Semi-Active Railway Suspension --- p.94 / Chapter 6.3.1 --- Lateral vibration on the train --- p.94 / Chapter 6.3.2 --- Semi-active control strategy --- p.95 / Chapter 6.4 --- Simulation Results --- p.98 / Chapter 6.4.1 --- Lower sway mode excitation --- p.99 / Chapter 6.4.2 --- Upper sway mode excitation --- p.105 / Chapter 6.4.3 --- Mixed sway mode excitation --- p.110 / Chapter 6.4.4 --- BR high speed assault course --- p.116 / Chapter 6.4.5 --- Discussions --- p.124 / Chapter 6.5 --- Effects of Vibration on Ride Comfort --- p.128 / Chapter 7. --- CONCLUSIONS --- p.134 / APPENDIX --- p.136 / BIBLIOGRAPHY --- p.142

It has been found that magneto-rheological (MR) devices can produce large controllable force/torque while consuming little power. In this research, an MR actuator that can function as a clutch or a brake is developed, in order to be applied to an assistive knee brace. The torque capability and dynamic characteristics of the MR actuator are evaluated. The relationship between the torque output and the applied coil current is given. The response time is also measured. Experimental results show that the MR actuator can provide enough torque for normal activities with sufficiently fast response. IP control and adaptive control are proposed to control the MR actuator. Experiments under these controls are carried out. With anti-windup strategies, both controls achieve good performances. However, adaptive control would be more promising since it can adapt to parameter variations and maintain good performance. An assistive knee brace that contains this MR actuator and a DC motor is developed. In order to study the performances of the knee brace before applied to human body, experiments are conducted for evaluation under a custom-built testing structure. IP-based state control and adaptive control are used to control both the MR actuator and DC motor. Experimental results demonstrate that the MR actuator and DC motor work well together to provide assistance as expected. Compared with that without MR actuator, the evaluation results show that the knee brace with MR actuator is more energy efficient during normal walking, while having better force controllability and safety. / by Chen, Jinzhou. / Adviser: Liao Wei Hsin. / Source: Dissertation Abstracts International, Volume: 73-01, Section: B, page: . / Thesis (Ph.D.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references (leaves 140-151). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Electronic reproduction. [Ann Arbor, MI] : ProQuest Information and Learning, [201-] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Abstract also in Chinese.

Introdução: A estabilidade fisica de sistemas emulsionados pode ser avaliada através de avaliação da distribuição de gotículas, propriedades reológicas, termoanálise, microscopia, entre outras técnicas. Objetivo: Avaliar a estabilidade fisica de emulsões obtidas com diferentes concentrações de emulsificantes aniônicos (A - cetil fosfato de potássio 3, 5 e 7%) e não-iônicos (N monoestearato de glicerila, 3, 5 e 7%), e a influência da transposição de escala de produção. Metodologia: Avaliação da distribuição das gotículas formadas através de difração de raio laser, análise reológica do tipo fluxo, microscopia e termogravimetria. Resultados e Conclusão: Os valores de 90% das gotículas foram menores que 92,66 µm; 50,28µm e 38,80µm, respectivamente para 3, 5 e 7% de emulsificante N. No sistema A, 90% das gotículas foram menores que 3,85µm; 4,89µm e 63,57µm, para 3, 5 e 7%, respectivamente. O aumento de escala de produção influenciou ambos os sistemas, com aumento de viscosidade: Sistema A: de 6,614 Pa.s para 81,55 Pa.s e Sistema N - de 3,366 Pa.s para 7,153 Pa.s no sistema N. Na análise TG, somente água livre pôde ser detectada no sistema N e, no sistema A, água interlamelar e livre puderam ser detectadas (inicial e em estabilidade) / lntroduction: The physical stability of emulsions can be evaluated through droplets distribution evaluation, rheological properties, thermal analysis, microscopy and others. Objective: Evaluate the physical stability of emulsions containg different concentrations of anionic (A - potassium cetyl phosphate 3, 5 e 7%) and non-ionic emulsifiers (N - glyceril monostearate, 3, 5 e 7%), and the influence ofthe scale-up processo Methodology: Evaluate the droplets distribution with laser diffraction, rheology analysis, microscopy and thermogravimetry (TG). Results and Conc1usion: The values of 90% of the droplets were below 92.66 µm, 50.28µm and 38.80µm, respectively for 3, 5 and 7% ofN emulsifier. For system A, 90% ofthe droplets were below 3.85µm, 4.89µm and 63.57µm, for 3, 5 and 7%. The scale-up process influenced both systems, with an increase in the viscosity on system A from 6.614 Pa.s to 81.55 Pa.s and from 3.366 Pa.s to 7.153 Pa.s for system N. ln the TG analysis, only bulk water could be detected in system N and, in the system A, both interlamellar and bulk water were detected (initial and stability).

A celulose é o polímero natural renovável disponível em maior abundância atualmente. Por possuir estrutura semicristalina, é possível extrair seus domínios cristalinos através de procedimentos que ataquem sua fase amorfa, como a hidrólise ácida, obtendo-se assim partículas cristalinas chamadas nanopartículas de celulose (NCs). Estas nanopartículas têm atraído enorme interesse científico, uma vez que possuem propriedades mecânicas, como módulo de elasticidade e resistência à tração, semelhantes a várias cargas inorgânicas utilizadas na fabricação de compósitos. Além disso, possuem dimensões nanométricas, o que contribui para menor adição de carga à matriz polimérica, já que possuem maior área de superfície, quando comparadas às cargas micrométricas. Nanocompósitos formados pela adição destas cargas em matrizes poliméricas podem apresentar propriedades comerciais atraentes, como barreira a gases, melhores propriedades térmicas e baixa densidade, quando comparados aos compósitos tradicionais. Como se trata de uma carga com dimensões nanométricas, obtida de fontes renováveis, uma das principais áreas de interesse para aplicação deste reforço é em biopolímeros biodegradáveis. O poli(ácido lático) (PLA), é um exemplo de biopolímero com propriedades mecânicas, térmicas e de processamento superiores a de outros biopolímeros comerciais. No presente trabalho foram obtidas nanopartículas de celulose (NCs), por meio de hidrólise ácida, utilizando-se três métodos distintos, com o objetivo de estudar o método mais eficiente para a obtenção de NCs adequadas à aplicação em compósitos de PLA. Os Métodos I e II empregam extração das NCs por meio do H2SO4, diferenciando-se apenas pela neutralização, a qual envolve diálise ou neutralização com NaHCO3, respectivamente. No Método III a extração das NCs foi realizada com H3PO4. As NCs foram caracterizadas por diferentes técnicas, como difração de raios X (DRX), análise termogravimétrica (TG), espectroscopia vibracional de absorção no infravermelho (FTIR), microscopia eletrônica de transmissão (MET) e microscopia de força atômica (MFA). Os resultados de caracterização das NCs indicaram que, a partir de todos os métodos utilizados, há formação de nanocristais de celulose (NCCs), entretanto, apenas os NCCs obtidos pelos Métodos II e III apresentaram estabilidade térmica suficiente para serem empregados em compósitos preparados por adição da carga no polímero em estado fundido. A incorporação das NCs em matriz de PLA foi realizada em câmara de mistura, com posterior moldagem por prensagem a quente. Compósitos obtidos por adição de NCs obtidas pelo Método II foram caracterizados por calorimetria exploratória diferencial (DSC), análise termogravimétrica, microscopia óptica, análises reológicas e microscopia eletrônica de varredura (MEV). A adição de NCs, extraídas pelo Método II, em matriz de PLA afetou o processo de cristalização do polímero, o qual apresentou maior grau de cristalinidade. Além disso, a adição de 3% em massa de NCs no PLA foi suficiente para alterar seu comportamento reológico. Os resultados reológicos indicaram que a morfologia do compósito é, predominantemente, composta por uma dispersão homogênea e fina da carga na fase matriz. Micrografias obtidas por MEV corroboram os resultados reológicos, mostrando, predominantemente a presença de partículas de NC em escala nanométrica. Compósitos de PLA com NCs obtidas pelo Método III apresentaram aglomerados de partículas de NC em escala micro e milimétrica, ao longo da fase matriz, e não foram extensivamente caracterizados. / Cellulose is the renewable natural polymer currently available in greatest abundance. Cellulose is a semicrystalline polymer, and it is possible to extract its crystalline domains through a procedure that destroys its amorphous phase, such as acid etching, so obtaining crystalline cellulose particles called cellulose nanoparticles (NC). These nanoparticles have attracted great scientific interest because they have mechanical properties similar to those of many inorganic types of filler used in polymer matrix composites, like elastic modulus and tensile strength. Moreover, they have nanometric dimensions, which contribute to lower filler contents in the polymer matrix, due to its increased surface area when compared to the one of micrometric fillers. Nanocomposites formed by adding these fillers into polymeric matrices can present attractive commercial properties such as gas barrier, improved thermal properties, and low density, when compared to traditional composites. As NC are nanometric scale fillers, obtained from renewable sources, there is a great interest in their application into biodegradable biopolymer matrixes. Poly (lactic acid), PLA, is an example of biopolymer that presents improved thermal, mechanical and processing properties, when compared to the ones of other commercial biopolymers. In this work, cellulose nanoparticles (NC) were obtained, via acid hydrolysis, using three different methods, in order to study the most efficient method to obtain NC suitable to be used in polymer matrix composites. NC obtention methods I and II employ extraction by H2SO4. Methods I and II differ only in the neutralization step, which involves dialysis, for Method I, and neutralization with NaHCO3, for Method II. In Method III, the extraction of the NCs was performed using H3PO4. The NC were characterized by different techniques such as X-ray diffraction (XRD), thermogravimetric analysis (TG), infrared absorption spectroscopy (FTIR), transmission electron microscopy (TEM) and atomic force microscopy (AFM). The characterization results indicated that all methods yielded cellulose nanocrystals. However, only NC obtained by methods II and III showed sufficient thermal stability to be used in composites prepared by melt mixing. The NC/PLA composites were prepared in a mixing chamber, followed by hot press molding. The composites with addition of NC obtained by Method II were characterized by differential scanning calorimetry (DSC), TG, optical microscopy, rheological analysis and scanning electron microscopy (SEM). The cellulose nanoparticles extracted by Method II affected the crystallization process of the PLA. The composite presented a higher degree of crystallinity than the pure matrix. Furthermore, the addition of 3 wt% of the NC in PLA was enough to change its rheological behavior. The rheological results indicated that the morphology is predominantly composed by a fine and homogeneous dispersion of the filler in the matrix. The SEM micrographs corroborate the rheological data, showing, predominantly, NC particles in nanometric scale. Composites with NC obtained by Method III presented micro and milimetric scale clusters of NC particles in the matrix phase and were not extensively characterized.

Thesis (MTech (Food Technology))--Cape Peninsula University of Technology, 2018. / The aim of this study was to produce Bambara groundnut (BGN) starch-catechin complex using chemical initiators (ascorbic acid and hydrogen peroxide) and cyclodextrin (alpha and beta) with the view to obtain a functional ingredient for the food industry. BGN starch was successfully extracted from BGN flour through dry milling method, yielding 32% of BGN starch. Native BGN starch was chemically modified using ascorbic acid (1% w/w) and hydrogen peroxide (165% w/w) as redox, biocompatible initiator for grafting catechin to the BGN starch. In addition, cyclodextrin (alpha and beta) were also used as initiators for modifying BGN starch through complexation methods. Complexation methods used included the microwave, co-evaporation and kneading. The characterization of native and modified BGN starches was carried out by performing scanning electron microscopy, powder X-ray diffraction, Fourier Transform Infrared (FTIR) and fluorescence spectroscopy analysis. Functional, thermal and rheological properties of native and modified BGN starches were evaluated. The pasting properties of BGN starches were determined using the Rapid Visco Analyser (RVA). According to the SEM profile, native BGN starch had round, oval and elliptical shapes typical for legume starches. Native BGN starch displayed a typical type-C crystallinity which is common among legumes with strong peaks at 2θ of 15o, 17o and 23o. BGN starches modified through complexation methods had sharper peaks indicating an increase in starch crystallinity; however, following chemical modification there was loss in starch crystallinity which was evidenced by the amorphous region in the chemically modified BGN starches. Structure of native and modified BGN starches was confirmed by FTIR. The FTIR spectra of native BGN starch showed variable peaks at 3285.34 cm-1, 2931.69 cm-1, 1634.36 cm-1, 1336.77 cm-1 which are attributed to OH stretching, C-H stretching, water bending vibrations and C-O stretching, respectively. Furthermore, the FTIR results confirmed that native BGN starch is made up of glucose molecules just like all other starches. All modified BGN starches displayed a new absorption peak at 1020 cm-1 wavelength, thus indicating that starch modification was successful. On the other hand, all BGN starch-catechin complexes displayed a new absorption peak in the range of 1520 -1560 cm-1, attributed to the C-C stretching within the aromatic ring of the catechin. The successful grafting of catechin to BGN starch was also confirmed by the fluorescence spectroscopy results, where all the BGN starch-catechin complexes had an emission peak at 320 nm while native BGN starch had an emission peak at 270 nm. Antioxidant capacity of BGN starch was determined through DPPH and ORAC antioxidant assays. Within the DPPH assay, the antioxidant activity ranged from 2.26 to 38.31 μmol TE/g. The antioxidant activity of modified BGN starch-catechin complexes was significantly (p ≤ 0.05) higher than the ones modified without catechin. On the other hand, within the ORAC assay, the antioxidant activity ranged from 0.07 to 126.71 μmol TE/g. As opposed to the results obtained in DPPH assay, the antioxidant activity of chemically modified BGN starch-catechin complexes was significantly (p ≤ 0.05) higher than that of complexed BGN starch-catechin complexes. Chemical modification significantly increased the swelling capacity of native BGN starch while complexation methods significantly reduced it.