The objective of this Thesis is to devise a system for the "rheology-based design" of non-settling (homogeneous) slurry pipelines that is more conducive to application by practicing engineers without impairing its accuracy or utility for research purposes. The cornerstone is the development of a new rheological model and constitutive equation for homogeneous slurry based on the aggregation/deaggregation of the suspended mineral particles. This “yield plastic” model is shown to describe a family of models that includes the Newtonian, Bingham plastic and Casson models as special cases. It also closely approximates the results of many consistency models, including power law, yield power law, Cross and Carreau-Yasuda. The yield plastic model is then used to develop design equations to determine the pressure-gradient of laminar and turbulent pipe flow. A relative energy dissipation criterion is proposed for the laminar-turbulent transition and shown to be consistent with currently used transition models for Newtonian and Bingham fluids. Finally, a new dimensionless group (the “stress number”) is proposed that is directly proportional to the pressure-gradient and independent of the velocity. When the design equations are presented graphically in terms of the stress number and the plastic Reynolds number, the resulting “design curve diagram” is shown to be a dimensionless (pressure-gradient vs. velocity) pipe flow curve. The net result is that the hydraulic design of homogeneous slurry systems only requires the use of a single constitutive equation and three engineering design equations. The results are presented in a conceptually easy form that will foster an intuitive understanding of non-Newtonian pipe flow. This will assist engineers to understand the impact of slurry rheology when designing, operating and troubleshooting slurry pipelines and, in the future, other slurry related processes. / Applied Science, Faculty of / Mining Engineering, Keevil Institute of / Graduate

A systematic research study was carried out in order to characterize the rheology of concentrated slurries prepared from eight nickel laterites. The experiments were carried out using a rotational viscometer, and the behavior of the laterites was evaluated in terms of the apparent viscosity and yield stress obtained through flow curve modeling. An attempt was made to correlate the results obtained for the laterite samples with data obtained for model single mineral systems as well as for model mixed mineral systems. In combination with detailed mineralogical characterization of the laterite samples, all the rheological results allowed a rheology-based laterite classification system to be proposed. Accordingly, the laterite samples gave the following responses: the SAPSIL samples (high-quartz) generally producedl ow yield stress values, the SAPFE samples (high-iron) were characterized by intermediate to high yield stress values, while the SAP samples (saprolite) gave the highest yield stress values. Interestingly, these dominant rheological responses of laterites could actually be predicted based on rheological tests carried out on model mineral suspensions (particularly goethite and quartz). Since the rheology of fine mineral suspensions is largely determined by the surface properties (surface charge) of the particles, a series of electro-acoustic measurements were also performed on model minerals and laterite samples to analyze the surface charge characteristics of the tested samples. It was demonstrated that the current electro-acoustic theory developed for single mineral systems can readily be used for modeling the behavior of mixed mineral systems. The modeling and experimental data agreed exceptionally well when constituent minerals were of the same surface charge under given pH. Clear but rather small deviations between experiment and theory were observed under conditions when the minerals were oppositely charged. This observation strongly suggested that inter-particle aggregation was most likely responsible for the observed discrepancies. Overall, the results of this thesis show that laterite slurries exhibit a wide range of rheological responses due to highly variable mineralogy, differences in particle size distributions, and difference in the surface properties of the many constituent minerals. It also shows that the surface properties of the minerals relates to rheology. / Applied Science, Faculty of / Mining Engineering, Keevil Institute of / Graduate

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The time dependent molecular motions of wood components at straining parallel to fibre direction were observed by infrared polarization technique. A two-stage molecular motion involving three wood components, cellulose, hemicellulose and lignin is suggested as the course of wood molecular relaxation. The first stage begins at equilibrium, when the specimen is not stressed, and extends immediately to a minimum dichroic ratio (formula omitted) of carbo-hydrate components represented by 1160 cm⁻¹ and 1730 cm⁻¹ bands, and the maximum dichroism of lignin (1500 cm⁻¹). The second stage starts at the end of the first stage and extends to equilibrium recovery. Regardless of the form of external excitation (creep or stress relaxation), and the time of excitation (ramp- or step-loading), the basic pattern of the two-stage molecular motion was followed, while damping of the molecules accompanied the whole rheological process. Thus, the wood macromolecular structure maintains an "internal state" of equilibrium on receiving external excitation. This equilibrium state is achieved by moving the carbohydrate and lignin components in opposite directions. The described pattern of molecular motion for a component in wood is a compensatory result from the interference of other components. Removing one or more components from wood changes the motion patterns of the remaining components. The conformation of cellulose in the specimen without the presence of lignin and hemicellulose is comparable to that of other synthetic linear polymers. Energy transfer system of wood was postulated as being due to the directional movement of molecular components which results in association and high steric interference between carbohydrates and lignin, similar to cross-linked chains of lignin and carbohydrates. This energy transfer system of wood is further facilitated by the existence of a systematic structure of wood microfibrils which permits a zone of gradual transition from high crystallinity to a diffuse state. The lignin network of the system may do more than transfer energy, it may act also as an "energy sink" and thereby function to maintain the memory of the excitation. / Forestry, Faculty of / Graduate

Orientadores: Antonio Carlos Bannwart, Vanessa Cristina Bizotto Guersoni / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica e Instituto de Geociências / Made available in DSpace on 2018-08-27T08:44:42Z (GMT). No. of bitstreams: 1 Geest_CharlieVanDer_M.pdf: 5712468 bytes, checksum: 765eb52c38dad02a122dbc8c5387f363 (MD5) Previous issue date: 2015 / Resumo: Os procedimentos de manutenção de equipamentos ou desligamento de emergência de uma unidade estacionária de produção de petróleo no mar ocorrem com freqüência na produção de petróleo. No caso de produção de petróleo parafínico escoando em uma linha de produção no fundo do mar, onde a temperatura é em torno de 4 ° C, a perda de calor podel conduzir o óleo a TIAC (Temperatura Inicial de Aparecimento de Cristais) do óleo. Isso leva à cristalização de parafinas. Dependendo do tempo que o óleo permaneça estático, neste ambiênte, perdendo calor, é possivel que se forme uma estrutura parafínica que bloqueie completamente a linha de produção. Linhas de produção com óleos parafínicos são um problema grave para a garantia de escoamento. É importante saber a pressão mínima necessária para reiniciar o escoamento para projetar as instalações de bombas na superfície. Óleos parafínicos são fluidos complexos e tem sido estudados há muito tempo. O comportamento reológico é um dos principais fatores que aumenta a complexidade do problema, no entando, para se prever o comportamento do óleo, o estudo de outros fenomênos é necessários, tais como compressibilidade e encolhimento térmico. Estudos experimentais foram feitos para estudar a reologia, compressibilidade e o encolhimento térmico, individualmente, em um reômetro Hakke Mars 3 e em uma celula PVT. Depois de todos os parâmetros estudados individualmente uma linha em escala reduzida foi construída para estudar o comportamento do óleo numa tubulação com a influência de todos os fenômenos físicos juntos. Todos os experimentos foram realizados com dois óleos reais parafínicos para melhor generalizar os resultados. O óleo apresenta o comportamento reológico denominado tixotrópia. Tixotropia é um fenômeno complexo e não é completamente compreendido pela comunidade científica, e foi definida pelo Dicionário de física de Oxford: "Certos materiais se comportam como sólidos sob pequenas tensões aplicadas, mas sob tensões maiores se tornam líquidos. Quando as tensões são removidas do material este volta para sua consistência inicial. Esta propriedade é particularmente associada com determinadas colóides que formam géis quando deixados em repouso, mas que se tornam líquidos quando mexido ou agitado, devido a uma redistribuição da fase sólida ". Neste estudo, o obetivo era simular o comportamento de dois óleos comerciais parafínico diferentes, com base nos resultados experimentais. A partir da revisão da literatura, o modelo de de Souza Mendez and Thompson (2013) foi selecionado para a reologia. O modelo não foi capaz de prever os dados perfeitamente, então, uma alteração foi feita para melhorar suas previsões, sem alterar o significado físico das equações. A abordagem matemática da linha foi feita com base no balanço de massa e quantidade de movimento, para simular os resultados da linha de produção foi feito um algoritmo baseado no método númerico das diferenças finitas. Um dos principais objetivos deste trabalho era simular a linha, baseado nas equações de conservação de massa e movimento, implementando o modelo elastico viscoplástico tixotrópico. Porém, como os resultados experimentais não mostraram um resultado onde a reologia era realmente relevante, a fase final do algoritmo considerou somente um fluido newtoniano fracamente compressível / Abstract: The Procedure of shutdown of an oil production unit for equipment maintenance or emergency occurs with high frequency during its operational lifetime. In the case of waxy crude oil production, when, the crude stays at the bottom of the sea at 4°C, the loss of heat leads to the WAT (Wax Appearance Temperature) of the oil, which leads to the crystallization of wax. If the oil stays static for sufficient time, it might form a structure that completely blocks the pipeline. Flow lines filled with gelled waxy crudes oil is a severe problem to flow assurance. It is important to know the minimum pressure necessary to restart the subsea flowline to design the surface pump facilities. Gelled waxy crudes are complex fluids and have been studied for a long time. One of the main factors that explain the complexity of the problems is the rheological behavior, though, in order to predict the minimum pressure, others physical parameters are required, such as compressibility and shrinkage. An experimental study was done with a rheometer to study the rheology, then, with the PVT cell to study the compressibility and the shrinkage. These parameters were studied individually and afterwards an apparatus was built to study the behavior of the oil in a pipeline were their influence were evalueted. All the experiments were performed with two waxy crudes oils to better generalize the results. The oil has a temporal rheological behavior defined as thixotropic. Thixotropy is a complex flow phenomenon and is not completely understood by the scientific community, and was defined by the Oxford Encyclopedic Dictionary of Physics as: "Certain materials behave as solids under very small applied stresses but under greater stresses become liquids. When the stresses are removed the material settles back into its original consistency. This property is particularly associated with certain colloids which form gels when left to stand but which become sols when stirred or shaken, due to a redistribution of the solid phase." In this study, the idea was to simulate the behavior of two different commercial waxy crude oils, based on the experimental results. From the literature survey, the model of Souza-Mendez-Thompson (2013) was chosen to evaluate the rheological behavior. The model was not able to predict the data perfectly, then, a modification was made to improve its predictions without changing the physical meaning of the equations. A mathematical approach was done based on mass and momentum balance to simulate the results of the pipeline with a difference finite method. The main goals of this study was to simulate the pipeline with an elasto viscoplastic thixotropic model within the algorithm based on mass and momentum equations. But, as the experimental results were showing that the rheological behavior was not a relevant phenomena in the restart process, the final phase of the algorithm was reconsider, since did not apply for our experimental data. The results considering the oil as a Newtonian fluid with high viscosity had good accuracy / Mestrado / Explotação / Mestre em Ciências e Engenharia de Petróleo

The presence of and interactions between structural defects, fluids, and trace elements during deformation play a vital role in the manner in which materials respond to an applied stress. Although the links between crystal defects and trace element mobility have been lying at the frontier of research in Earth sciences, the role of fluids and the underlying physico-chemical processes linking them remain poorly understood. Investigation of these nanometer scale processes requires a correlative approach combining high-spatial resolution analytical techniques. This thesis integrates novel 2D and 3D structural and geochemical mapping methods such as electron channeling contrast imaging, electron backscatter diffraction, scanning transmission electron microscopy (STEM) and atom probe tomography (APT) to interrogate the atomic structure and composition of geomaterials in an attempt to better understand long-standing questions in Earth sciences and build bridges between materials science and geoscience. The processes investigated in this thesis include: 1) the underlying diffusion processes that mobilize trace elements into deformation-induced nanostructures; 2) the mechanisms of trace element segregation associated with fluid inclusions; 3) the influence of fluid inclusions on the mobility of structural defects and trace element mobility; and 4) the initial stages of bubble nucleation in the presence of nanoscale chemical heterogeneities. Ultimately, this research interrogates the feedbacks between deformation and trace element diffusion processes, fundamentally investigating their impact on rheology. More specifically, the thesis investigates the influence of deformation and associated nanostructures on the remobilization of trace elements and, in turn, the influence of trace elements on the nucleation and mobility of nanostructures. The combined work successfully identified two diffusion mechanisms for deformation-induced trace element mobility, characterized fluid-inclusions in APT data, documented two processes that led to proposing a new fluid inclusion-induced hardening model, and documented direct evidence of bubble nucleation on the surface of nanoscale chemical heterogeneities. This work not only pushes the limits of high-spatial resolution analytical techniques including STEM and APT, but the results have significant transdisciplinary implications in the fields of geoscience, materials science, engineering, and analytical microscopy.

This Diploma thesis deals with optimization of the hydrogel preparation with various additions of substances affecting adhesion, studying the adhesion of prepared hydrogel systems and modifying their adhesion properties. Prepared hydrogels were agarose, alginate and gellan polymer systems with additions of acrylic acid, acrylamide, calcium chloride and Tween 20. The experimental part of the diploma thesis focuses first on optimizing the preparation of individual hydrogels, from which, according to certain criteria, suitable representatives were selected to study adhesion and its controlled modification. Agarose and gellan hydrogels were selected as suitable representatives, which were then used in rheological measurements. Based on these measurements, the effect of the adhesive force and the adhesive work of individual materials was evaluated. It was found that the best adhesion properties of the materials used are unadjusted hydrogels, in the case of hydrogels with the addition of another substance, a negative effect on adhesion was observed, when the adhesion force was reduced and also the adhesion work was reduced.

Thesis. 1977. M.S.--Massachusetts Institute of Technology. Dept. of Nutrition and Food Science. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Bibliography : leaves 72-76. / M.S.

Soft materials are ubiquitous in every aspect of our daily life. These materials composed of a wide range of subfields including surfactants, foams, emulsions, pastes, slurries, polymers, gels, and colloidal suspensions. In recent years, there has been a great interest focusing on the understanding of the macroscopic properties of various types of soft materials as a function of their microstructures. For example, the structure-property relationship of physically-associating triblock copolymer gels can be controlled by selecting different types of solvents and changing the temperature. In these systems, gelation occurs due to the significant changes in the solubility of one or more of the blocks with temperature compared to the other blocks. Therefore, changing the temperature can lead to the structural transitions and macroscopic properties. The other strategy that can be used to modify the macroscopic performance of polymer gels is through the incorporation of nanoparticles, such as graphene nanoplatelets and nanotubes. The addition of nanoparticles can also affect the mechanical properties of concentrated suspensions in which, understanding the structure/flow properties is vital for processing and manufacturing of a product. Despite significant advances in the field of soft materials, our understanding in linking the structure-property relationships of polymer gels and concentrated suspensions is incomplete. With this perspective, in this dissertation, shear-rheometry and scattering techniques were used to understand the structural changes of the self-assembled triblock copolymer gels over a wide length-scale and broad temperature-range. Graphene nanoplatelets have been incorporated into this system to investigate the self-assembly behavior and mechanical properties as a function of graphene concentration. On the other hand, in concentrated suspensions of functionalized nanoparticles in a low-molecular- weight polymeric media, the effect of nanoparticles on the rheological properties were investigated. The present work provides a better understanding of the nanoparticles’contributions on microstructure and mechanical behavior of soft materials.

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