No description available.

In this thesis, glucose responsive hydrogels based on cross-linked dextran molecules were studied to determine the diffusion rate of an insulin analogue. Investigations of the interaction between concanavalin A and dextran, both in free solution and in the form of glucose responsive hydrogels were conducted. The free solution results have shown that there is an increase of association constant between concanavalin A and dextran when the molecular mass of the dextran is increased. Free solution viscometric tests have shown that increasing the molecular mass or the concentration of the dextran increases the viscosity. The hydrogels have been shown to form for dextrans of molecular mass 43kD or greater. Experiments conducted with hydrogel membranes in a diffusion cell have shown that the batch to batch reproducibility of hydrogel transport properties is low. However, clear evidence of glucose enhanced transport was obtained and these results were compared with predictions obtained from a theoretical model of gel permeability that accounts for competitive displacement of affinity cross links. Oscillatory rheological tests of gelation mixtures which showed an increase in complex viscosity at the gel point with increasing molecular mass of dextran were in agreement with empirical observations that gels formed from the highest molecular mass dextrans were more physically robust and easier to handle. Swelling rate experiments have shown that the rate of hydration of a hydrogel in the presence of glucose is decreased due to the osmotic pressure of the glucose. This work has shown that the multivalent nature of concanavalin A may not be a necessary pre-requisite for this type of hydrogel due to spatial constraints decreasing the number of potential affinity bonds per tetramer. In-house production of more tightly defined dextrans might be expected to reduce heterogeneity and improve the reproducibility of this type of hydrogel membrane.

Master of Science / Department of Grain Science and Industry / Sajid Alavi / This study relates raw material particulate rheology to the granular flow in a single screw food extruder. Raw materials based on corn (i.e. meal, flour, and starch), wheat (i.e. farina, flour and starch), and sucrose (i.e. granulated, superfine, and powdered) were used as model particulate systems for the study. Various particulate-scale characteristics and flow parameters of these nine materials were determined using a powder rheometer. Properties such as basic flow energy, cohesion, flow function, and effective angle of internal friction were good indicators of flowability in an extruder. Corn meal exhibited lower energy requirements and a higher propensity for flow than corn flour (6.7mJ/g versus 10.7mJ/g, and “free-flowing” versus “cohesive,” according to Flow Function classifications), with wheat farina showing similar results when compared to wheat flour (5.8mJ/g versus 7.9mJ/g, and “highly free-flowing” versus “cohesive”), although both wheat systems showed lower energy requirements than their comparable corn systems. Sugar, being of a different base material and particle shape, behaved differently than these starch-based materials—flow energy decreased and propensity to flow increased as particle size decreased (51.7mJ/g versus 8.0mJ/g, and “free flowing” versus “highly free-flowing”). This large energy requirement for coarse sugar particles was attributed more to particle shape than composition, as the sharp edges of sugar can interlock and restrict movement through the sample. The starch-based results were validated in a particulate flow study involving the above model systems (corn meal, corn flour, wheat farina, and wheat flour) in a pilot-scale single screw extruder. Visualization data, obtained using a transparent plexiglass window during extrusion, confirmed that the flours exhibited higher flow energy requirements and a lower flow factor compared to coarser-particle size during extrusion, seen by the increased peak heights and barrel fill. Additionally, moisture changes were analyzed, showing an increase in energy required for starch-based materials as moisture increases and a decrease in energy for sucrose. Due to the hygroscopic nature of sucrose, moisture was absorbed more rapidly than starch products and the edges of individual particles softened, forming a soft solid. These physiochemical differences resulted in decreased energy requirements for sucrose as moisture was increased (51.7mJ/g to 13.6mJ/g), while corn meal and wheat farina yielded increased energy requirements (6.7mJ/g to 9.1mJ/g and 5.8mJ/g to 9.5mJ/g, respectively). Again, results of starch-based materials were validated using a plexiglass cover during extrusion, clearly showing an increase in barrel fill as moisture content increased for both materials, with corn meal flowing more readily than farina. Lastly, temperature of corn meal and farina was increased to show the difference in behavior of starch-based materials, where farina decreased in energy as temperature increased (14.4mJ/g to 12.1mJ/g ) while corn meal energy requirements increased (12.9mJ/g to 17.2mJ/g). With the results developed from these three experiments, and validated where physically possible, it was concluded that offline powder rheometry is a useful tool for predicting the behavior of food powders. These results were then developed into a computer-simulated model to allow for virtual and visual representation of the conveying action inside an enclosed steel barrel.

Various properties of the components and adhesives were modelled. The compatibility of the components were successfully incorporated into an extended Fox equation to predict the glass transition temperature. The peel strength of the adhesive was modelled in terms of the rheological properties of elastic moduli and loss tangent values at different temperatures. A second model based upon the value of the loss tangent at room temperature was also broadly successful but deviations from predicted behaviour were observed which were attributable to failure of the adhesive joints by a mode not included in the model. The modulus of the adhesive was modelled on the basis of an extended mixture rule in which the extent of compatibility was identified by a parameter n. The value of n varied as a function of adhesive composition and temperature, indicating that the behaviour of the adhesives changed subtly as the compatibility of the phases changed. The value of the parameter could not be directly related to the morphology of the adhesive phases. Fourteen commercially available poly(ethylene-co-vinyl acetate) (EVA) copolymer samples were selected in which there was a systematic change in the melt index, amount of vinyl acetate, and degree of crystallinity. Various hot melt adhesives were made using these copolymers and a standard amount of wax and resin. The materials were examined using differential scanning calorimetry (DSC), oscillatory rheometry (both controlled strain and controlled stress), and transient (creep) rheometry. The adhesives were also investigated using a variety of industrial tests which included peel adhesion and tensile testing at four different rates, open and setting time, shear and peel stress resistance at elevated temperatures, and viscosity determination over a wide range of temperatures. Detailed thermal analysis and characterisation have provided a range of accurate and systematic data on all of the materials and in particular showed that the components of the adhesive did not merely act as a mechanical mixture but had a distinct compatibility. The controlled stress technique was found to more discriminatory than the controlled strain, due to the more precisely controlled heating and cooling of the sample during loading and evaluation. Other key differences between the techniques are attributable to the different thermal histories imposed upon the semi-crystalline adhesive components. Detailed analysis of the complex rheological curves showed several key factors. One of the most important was the modulus crossover temperature Tx which was shown to correlate well with the softening point of the adhesive, its open time, and the heat resistance under shear as determined by the shear adhesion failure temperature (SAFT). It was possible to construct a linear relationship between Tx and SAFT which allowed prediction of this key adhesive parameter. There was no significant relationship established between the softening point of an adhesive and its heat resistance, open time, or critical thermal characteristics, and the use of the softening point as a useful indicator of adhesive performance is contested. The open time was shown to be clearly influenced by the properties of the copolymer. The relationship between open time and melt index is complex and two competing mechanisms are thought responsible. These are the inability to fully wet the substrate for high molecular weights and resistance to complete substrate penetration by capillary effects for adhesives formulated with low molecular weight polymers. Both of these effects cause a reduction in open time. The cloud points of the adhesives were independent of the molecular weight but strongly affected by composition. Degree of crystallinity was also an influence at higher molecular weights. Cloud point correlated slightly with the onset of crystallisation as determined by DSC however differences are extremely small and the method was not deemed robust enough for widespread industrial application. Various properties of the components and adhesives were modelled. The compatibility of the components were successfully incorporated into an extended Fox equation to predict the glass transition temperature. The peel strength of the adhesive was modelled in terms of the rheological properties of elastic moduli and loss tangent values at different temperatures. A second model based upon the value of the loss tangent at room temperature was also broadly successful but deviations from predicted behaviour were observed which were attributable to failure of the adhesive joints by a mode not included in the model. The modulus of the adhesive was modelled on the basis of an extended mixture rule in which the extent of compatibility was identified by a parameter n. The value of n varied as a function of adhesive composition and temperature, indicating that the behaviour of the adhesives changed subtly as the compatibility of the phases changed. The value of the parameter could not be directly related to the morphology of the adhesive phases.

Cure time is often the bottleneck of composite manufacturing processes, therefore it is important to understand the cure of today's thermosetting adhesives. This research attempts to characterize the cure rate of two commercial phenol-formaldehyde adhesives. Two methods are used, parallel-plate rheometry and dielectric spectroscopy. Viscosity data from a parallel-plate rheometer may be used to track the advance of polymerization as a function of temperature. This data can then be used to optimize press conditions and reduce production times and costs. The research will further examine resin cure through dielectric analysis; such a technique could monitor resin cure directly and in real-time press situations. Hot-pressing processes could conceivably no longer require a set press schedule; instead they would be individually set based on dielectric data for every press batch. Such a system may lead to a more efficient and uniform product because press times could be based on individual press cycles instead of entire product lines. A more likely scenario, however, is the use of in situ adhesive cure monitoring for troubleshooting or press schedule development. This research characterized the cure of two phenol-formaldehyde resins using parallel-plate rheometry, fringe-field dielectric analysis, and parallel-plate dielectric analysis. The general shape of the storage modulus vs. time curve and the gel and vitrification points in a temperature ramp were found. Both dielectric analysis techniques were able to characterize trends in the resin cure and detect points such as vitrification. The two techniques were also found to be comparable when the cure profiles of similar conditions were examined. / Master of Science

[pt] O escoamento cisalhante oscilatório de grande amplitude (large amplitude oscillatory shear - LAOS) é considerado atualmente uma das metodologias mais promissoras para caracterização de materiais complexos. Como uma grande faixa de processos industriais envolve grandes deformações é de extrema importância entender como esses materiais se comportam mecanicamente sob essas circunstâncias para o correto projeto e operação. Através de uma caracterização reológica completa de um material elastoviscoplástico mostramos que o modelo de Jeffreys é adequado para interpretar fisicamente os resultados em LAOS de materiais complexos. Conforme a amplitude de tesão e frequência são variados independentemente, dois tipos de movimento, caracterizados por respostas não senoidais e senoidais, foram observados respectivamente: i) movimentos a estrutura variável, quando a amplitude de tensão é maior que a tensão limite de escoamento do material, e ii)movimentos a estrutura constante, para casos onde a amplitude de tensão é menor que a tensão limite ou onde a frequência é muito maior que o inverso do tempo característico do material. Assim, uma nova metodologia, a quasi-linear LAOS (QL-LAOS) foi desenvolvida para a caracterização reológica e interpretação de resultados em LAOS. Ademais, foi obtida excelente concordância entre as previsões teóricas e os resultados experimentais. / [en] Large amplitude oscillatory shear flow (LAOS) is presently considered one of the most promising methodologies to investigate the behavior of complex materials. Since a wide range of industrial processes involves large deformations, understanding how complex materials behave under these conditions is fundamental for operation and design purposes. By performing a thorough rheological characterization of a commercially available hair gel, it was shown that a Jeffreys framework is suitable to interpret physically LAOS rheology data of complex materials. As the stress amplitude and frequency are independently varied, two classes of motion are observed, characterized by a non-sinusoidal and a sinusoidal response, respectively: structure-changing motions, when the stress amplitude is above the yield stress and the frequency is of the order of the reciprocal of the thixotropic characteristic time; and constant-structure motions, when either the stress amplitude is below the yield stress or the frequency is much larger than the reciprocal of the thixotropic characteristic time. Thus, a novel methodology, the quasi-linear LAOS (QL-LAOS) methodology, is suggested for rheological characterization and interpretation of LAOS results. Moreover, a remarkable agreement between the theoretical predictions and experimental results was obtained.

[pt] Os hidratos de gás natural são sólidos cristalinos, semelhantes ao gelo, formados pela associação de moléculas de água e de gás numa determinada estrutura organizada. Sua ocorrência é uma preocupação inegável para a Indústria de Petróleo e Gás, dado o risco potencial de garantia de escoamento, podendo ocasionar paradas não programadas em operações como a perfuração e produção. Portanto, grandes investimentos são feitos a fim de prevenir a formação de hidratos. No entanto, os cenários cada vez mais desafiadores de produção de petróleo estão incentivando a busca de metodologias de avaliação de risco, procurando identificar as condições para a formação de hidratos, mas com pouca possibilidade de entupimento. Neste contexto, o entendimento de reologia de hidratos é um elemento chave, pois permite detectar a formação do hidrato a partir de variações das propriedades reológicas. Entretanto, uma dificuldade desta abordagem ocorre devido à condição necessária para a formação de hidrato, a combinação de alta pressão e baixa temperatura. Este trabalho se insere neste contexto: para avaliar o processo de formação de hidrato em condições mais favoráveis utiliza-se em geral um fluido modelo que forma hidratos à pressão atmosférica. Este trabalho visa analisar os efeitos dos cortes de água e de tensoativos na viscosidade, nos módulos de armazenagem e dissipação de um fluido modelo, uma emulsão de água-em-óleo. A formação de hidrato ocorre com a adição de ciclopentano a este modelo de emulsão. / [en] Natural gas hydrates are solid crystalline, similar to the ice, formed by the association of water molecules and gas of a given organized structure. Its occurrence is an undeniable concern for Oil and Gas, given the potential risk of flow assurance and may cause unscheduled downtime in operations, such as drilling and production. Therefore, large investments are made in order to prevent the formation of hydrates. However, the increasingly challenging scenarios of oil production are encouraging the pursuit of new methodologies for risk assessment, seeking to identify the conditions hydrates will form, but with little chance of clogging. In this context, the understanding of rheology of hydrate is a key element, it allows detecting the formation of hydrate as of changes in rheological properties. However, a difficulty of this approach occurs due to need for hydrate formation conditions, the combination of high pressure and low temperature. This work fits in this context: to evaluate the process of hydrate formation on conditions more favorable is used usually a fluid model that form hydrates at atmospheric pressure. This work aims to analyze the effects of the water cuts and surfactants on viscosity, in storage and dissipation modules of model fluid water emulsion in oil. The hydrate formation occurs adding on this model fluid cyclopentane.

Os escorregamentos causados por precipitação intensa ocasionam grandes prejuízos a cada estação chuvosa no sudeste brasileiro. Essa dissertação estudou 2 amostras de solos da região serrana do Rio de Janeiro sob uma nova ótica de análise para escorregamentos. As amostras foram coletadas 4 meses após a ocorrência do megadesastre, onde chuvas com precipitação de 325mm em 48 horas causaram mais de 1500 mortes. Em relatos e vídeos obtidos de movimentos de massa que ocorreram nesse evento foi possível observar que o solo apresentou comportamento de um líquido denso e viscoso, escoando pelas encostas da cidade, ou seja, o solo, encharcado pelas chuvas intensas que ocorreram na região, sofreu liquefação. Esse material viscoso formado pela mistura de solo+água que foi caracterizado através da utilização da reologia. Para isso foram apresentados os conceitos da reologia e dos ensaios reométricos, e as possíveis aplicações para solos e na caracterização de corridas de lama. Foram utilizados três ensaios para caracterizar o solo no estado fluido, que foi o squeeze flow, o reômetro de torque com reometria planetária, e o reômetro de placas paralelas. O principal objetivo para utilização desses ensaios é a praticidade para realização dos ensaios, que tem como características: a rapidez na execução, a coleta de dados é realizada automaticamente, apresentam receptibilidade e a facilidade na execução. Com os resultados obtidos foi possível observar a mudança de comportamento do solo (de um material com comportamento elástico para um material como um fluxo de lama) com a elevação da umidade, para os dois ensaios. Os resultados demonstram que o valor do limite de liquidez calculado através do aparelho de Casagrande é confirmado com esses novos aparelhos, ii sendo que, para esses aparelhos é visível a mudança de comportamento que define o limite de liquidez. Através dos resultados também foi possível determinar que o solo em estado fluido tem seu comportamento regido pelo modelo de Herschel Bulkley. Para tornar os resultados obtidos aplicáveis foi apresentado um capítulo ligando os resultados obtidos da reometria com a possibilidade do solo sofrer liquefação, aliado com os resultados obtidos dos ensaios de caracterização geotécnica. Sendo realizadas análises de estabilidade com os resultados obtidos, correlacionando a inclinação do talude, o nível dágua e a ocorrência da liquefação. / Landslide caused by rainfalls cause major damage each rainy season in southeastern Brazil. This dissertation studied two soil samples from the mountainous region of Rio de Janeiro in a new light analysis for landslides. Samples were collected four months after the occurrence of disaster, when rainfall with intensity of 325mm in 48 hours caused more than 1,500 deaths. In reports and video obtained from mass movements that occurred at this event was observed that the soil responded as a dense liquid, viscous draining the citys landscape. The drenched soil, by heavy rains that occurred in the region, suffered liquefaction. This viscous material formed by mixture of soil and water that was characterized by the use of rheology. In this dissertation was presented the concepts of rheology and rheometric tests for application in soils and characterization of fluid movements. Tree different rheometric tests were performed to characterize the soil in the fluid state, which was the squeeze flow, torque rheometer with planetary geometry and parallel plate rheometer. The main objective of these tests is to use the convenience for the tests, that presents the follow characteristics: the speed of execution, data collection is performed automatically and the testes present repeatability apart from ease of application. With the results we observed the change of soil behavior (of a material with elastic properties for a material that presents the behavior as a mud flow) with increasing humidity for the tests. The results show that the value of the liquidity limit calculated by the Casagrande apparatus is confirmed with these new devices, furthermore with the use of these devices is visible the behavior change that defines the liquid limit. iv Was determined that the Herschel Bulkley model is the one that best represents the behavior of the soil in the fluid state. Was presented a chapter with an application of the results obtained by adding the results of the rheometer with the results of geotechnical characterization tests to determine the possibility of soil suffer liquefaction. To this aim, were performed stability analysis considering the results obtained, correlating the slope inclination, the water level and the occurrence of liquefaction.

The rheological behavior analysis of Engineered Cementitious Composites (ECC) is key to understand how the different preparation techniques affect the composite mechanical performance. However, the rheological assessment of reinforced materials becomes more complex since fibers usually cause flow disturbances not found in nonreinforced cementitious materials. Besides that, simple workability measurement techniques are not able to fully understand the composite behavior in the fresh state creating the need for more precise techniques to be employed. The main objectives of this study were to evaluate the ECC rheological behavior using different rheometer devices (Vane system and Ball measuring system) and investigate the influence of mixing processes on the fiber homogenization and rheological behavior. Additionally to this, a link between rheological behavior and mechanical performance was investigated. In the end, the ball measuring system revealed to be more efficient than the vane system when evaluating the composite rheological behavior. In addition, the mixing process influenced the rheological behavior of PVA-ECC especially regarding the moment which fibers are added. Fiber addition after mortar mixture improved fibers homogenization and reduced mixing energy by around 8%. Moreover, a correlation between rheological and mechanical properties showed that a 2-times variation in either yield stress or viscosity can lead to a variation of more than 50% in flexural strength without significantly affecting the composite compressive strength. It was also found that the lower the composite yield stress and viscosity the higher was its ultimate strain. To conclude, all those parameters contributed to understand the composite rheological behavior and globally optimize its performance. / Sem resumo

Os escorregamentos causados por precipitação intensa ocasionam grandes prejuízos a cada estação chuvosa no sudeste brasileiro. Essa dissertação estudou 2 amostras de solos da região serrana do Rio de Janeiro sob uma nova ótica de análise para escorregamentos. As amostras foram coletadas 4 meses após a ocorrência do megadesastre, onde chuvas com precipitação de 325mm em 48 horas causaram mais de 1500 mortes. Em relatos e vídeos obtidos de movimentos de massa que ocorreram nesse evento foi possível observar que o solo apresentou comportamento de um líquido denso e viscoso, escoando pelas encostas da cidade, ou seja, o solo, encharcado pelas chuvas intensas que ocorreram na região, sofreu liquefação. Esse material viscoso formado pela mistura de solo+água que foi caracterizado através da utilização da reologia. Para isso foram apresentados os conceitos da reologia e dos ensaios reométricos, e as possíveis aplicações para solos e na caracterização de corridas de lama. Foram utilizados três ensaios para caracterizar o solo no estado fluido, que foi o squeeze flow, o reômetro de torque com reometria planetária, e o reômetro de placas paralelas. O principal objetivo para utilização desses ensaios é a praticidade para realização dos ensaios, que tem como características: a rapidez na execução, a coleta de dados é realizada automaticamente, apresentam receptibilidade e a facilidade na execução. Com os resultados obtidos foi possível observar a mudança de comportamento do solo (de um material com comportamento elástico para um material como um fluxo de lama) com a elevação da umidade, para os dois ensaios. Os resultados demonstram que o valor do limite de liquidez calculado através do aparelho de Casagrande é confirmado com esses novos aparelhos, ii sendo que, para esses aparelhos é visível a mudança de comportamento que define o limite de liquidez. Através dos resultados também foi possível determinar que o solo em estado fluido tem seu comportamento regido pelo modelo de Herschel Bulkley. Para tornar os resultados obtidos aplicáveis foi apresentado um capítulo ligando os resultados obtidos da reometria com a possibilidade do solo sofrer liquefação, aliado com os resultados obtidos dos ensaios de caracterização geotécnica. Sendo realizadas análises de estabilidade com os resultados obtidos, correlacionando a inclinação do talude, o nível dágua e a ocorrência da liquefação. / Landslide caused by rainfalls cause major damage each rainy season in southeastern Brazil. This dissertation studied two soil samples from the mountainous region of Rio de Janeiro in a new light analysis for landslides. Samples were collected four months after the occurrence of disaster, when rainfall with intensity of 325mm in 48 hours caused more than 1,500 deaths. In reports and video obtained from mass movements that occurred at this event was observed that the soil responded as a dense liquid, viscous draining the citys landscape. The drenched soil, by heavy rains that occurred in the region, suffered liquefaction. This viscous material formed by mixture of soil and water that was characterized by the use of rheology. In this dissertation was presented the concepts of rheology and rheometric tests for application in soils and characterization of fluid movements. Tree different rheometric tests were performed to characterize the soil in the fluid state, which was the squeeze flow, torque rheometer with planetary geometry and parallel plate rheometer. The main objective of these tests is to use the convenience for the tests, that presents the follow characteristics: the speed of execution, data collection is performed automatically and the testes present repeatability apart from ease of application. With the results we observed the change of soil behavior (of a material with elastic properties for a material that presents the behavior as a mud flow) with increasing humidity for the tests. The results show that the value of the liquidity limit calculated by the Casagrande apparatus is confirmed with these new devices, furthermore with the use of these devices is visible the behavior change that defines the liquid limit. iv Was determined that the Herschel Bulkley model is the one that best represents the behavior of the soil in the fluid state. Was presented a chapter with an application of the results obtained by adding the results of the rheometer with the results of geotechnical characterization tests to determine the possibility of soil suffer liquefaction. To this aim, were performed stability analysis considering the results obtained, correlating the slope inclination, the water level and the occurrence of liquefaction.