Understanding the interactions of polymer interfaces is essential to improve polymer-based designs, as the properties of the interface are often different than those of the bulk material. This thesis explores the interfacial interactions of polymer interfaces for two classes of materials, additive manufacturing materials and fiber-reinforced composites. Additive manufacturing (AM) refers to a number of processes which rely on data generated from computer-aided design (CAD) programs to construct components by adding material in a layer-by-layer fashion. AM continues to generate a substantial amount of interest to produce fully functional products while reducing tooling costs associated with traditional manufacturing techniques such as casting and welding. Recent advancements in the field have led to the production of multi-material printing that has the potential to create products with enhanced mechanical properties and additional functionality. This thesis attempts to characterize the fracture resistance of AM materials produced by the PolyJet process. Test standards established for mode I fracture testing of adhesive joints are adapted to evaluate the fracture resistance and interface between two printed acrylic-based photopolymers. Significant differences in fracture energy and loci of failure between the selected test configurations were observed depending on the print orientation. Failures were nominally seen to occur at the interface, alternating from one adherend interface to another in a random fashion. Results demonstrated a decreasing trend in fracture energy at slower crack propagation rates, indicating that such dependency is associated with the fracture resistance of the interface. T-peel tests conducted on specimens prepared with both constant and graded interlayers revealed enhanced peel resistance with gradient interlayers, suggesting design opportunities of enhanced fracture toughness by implementing intricate material patterns at the interface of the two photopolymers. Fiber reinforced composite (FRCs) materials have become increasingly desirable in a number of industrial applications where weight reduction is critical for increased payloads and higher performance. When manufacturing structures from these materials, the presence of friction in the composite forming process is seen to have a major effect on the finished quality. Friction between the plies, or between the composite laminate and forming tool, can be undesirable as shape distortions such as wrinkles can appear and compromise the structural integrity of the finished product. To evaluate these frictional processes, a standard rheometer is used to evaluate tool-ply friction on dry textile fabrics and graphite/epoxy prepregs over a range of temperatures, pressures, and sliding velocities. The results provide some general insights into the frictional response of composite prepregs as a function of the manufacturing environment. The materials tested are shown to have different mechanisms that govern the frictional processes. In particular, the results of friction testing on the prepreg indicate that friction comes from a contribution of both Coulomb and viscous-related mechanisms, the latter which become especially at higher temperatures. / Master of Science

Le but principal de cette étude était d'évaluer et de mieux comprendre l'impact de la vitesse superficielle de gaz et des propriétés de boues activées (BA), sur leur comportement rhéologique et le transfert de l'oxygène dans des bioréacteurs.Tout d'abord, la rhéologie des BA a été évaluée à l'aide d'un rhéomètre tubulaire, conçu et construit dans ce travail. Des mesures rhéologiques ont été effectuées avec des BA provenant de cinq stations d'épuration (STEP) et avec des concentrations en MES comprises entre 2.3 et 10.2 g L-1. Selon ces résultats, la rhéologie des BA est significativement déterminée par la concentration en matière en suspension (MES) mais d'autres caractéristiques liées à leur origine, tel que la taille, la cohésion et la densité du floc, peuvent aussi influencer la viscosité apparente des boues. Basé sur les rheogrames expérimentaux, le modèle rhéologique issu de cette étude est comparé à des modèles rhéologiques existants.Deuxièmement, le transfert d'oxygène a été évalué dans une colonne à bulles (Hc=4.4 m, Dc=0.29m) installée dans deux STEP: une installation classique et un bioréacteur à membrane. La colonne, alternativement équipée d'un diffuseur fines ou grosses bulles (FB, GB), a été alimentée en continu avec des BA extraites du réacteur d'aération, ou de la boucle de recirculation ou du réacteur membranaire. Pour des MES comprises entre 3.0 et 10.4 g L-1, le coefficient kLa a étéplus faible dans les BA que dans l'eau propre et encore réduit avec une augmentation des MES. Cette diminution est en partie attribuable à la réduction observée de la rétention de gaz (εG), associée à une augmentation de la viscosité apparente des boues, celle-ci entrainant une réduction de l'aire interfaciale spécifique (a) due à la coalescence de bulles et à la formation de bulles plus grosses. Aussi, la concentration des tensioactifs non ioniques, a montré un effetnégatif sur le coefficient kLa lors des tests d'oxygénation effectués en aération FB et faibles concentrations en MES. Cet impact n'a pas été observé dans des conditions d'aération GB, ce qui a été expliqué par le taux de renouvellement d’interface plus élevé généré par ces dernières. Enfin, le taux de cisaillement moyen exercé par l'essaim de bulles dans la colonne pendant les tests d’oxygénation a été théoriquement évalué compte tenu des conditions d’opération. Par lasuite, des corrélations empiriques ont été construites en utilisant des nombres adimensionnels et expriment le coefficient kLa en fonction de la vitesse superficielle de gaz et la viscosité apparente, tout en considérant sa dépendance du taux de cisaillement. Enfin, le facteur alpha est défini comme une loi de puissance décroissante en fonction de la viscosité apparente, pour des systèmes à faible chargé. / The main purpose of this study was to evaluate and better understand the impact of superficial gas velocity and activated sludge properties,on activated sludge rheology and oxygen transfer in bioreactors. First of all, activated sludge rheology was evaluated using a tubular rheometer, designed and constructed in this work. Rheological measurements were performed with activated sludge from five different wastewater treatment plants and with MLSS concentrations between 2.3 and 10.2 g L-1. Results showed that although the sludge rheology is significantly defined by the MLSS concentration, other sludge characteristics related to the sludge orign, such as such as floc size, floc cohesiveness and floc density also influence the sludge apparent viscosity. Existing rheological models were evaluated on the set of obtained experimental flow curves. Besides, the oxygen transfer is evaluated in a bubble column (Hc=4.4, Dc=0.29 m) installed in two different wastewater treatment plants: a conventional activated sludge plant (CAS) and a membrane bioreactor (MBR). The column, alternatively equipped with a fine or a coarse bubble diffuser (FB, CB), was continuously fed with activated sludge extracted either from the aeration tank, the recirculation loop or the membrane reactor. With MLSS concentrations from 3.0 to 10.4 g L-1, the kkllaa coefficient was lower in activated sludge than in clean water and still reduced with an increase of the MLSS concentration. This reduction is partially attributed to the observed reduction of gas holdup (εεɢɢ), associated with an increase in the sludge apparent viscosity (µµαααααα), which leads to a reduction of the specific interfacial area (αα) due to bubble coalescence and the formation of larger bubbles. Besides, the concentration of non-ionic surfactants, exhibited a negative effect on the κκιιαα coefficient for the oxygenation tests performed under FB aeration conditions and low MLSS concentration. This impact was not observed under CB aeration conditions, which was explained by the higher renewal rates generated by coarse bubbles. Finally, the mean shear rate exerted by the bubble swarm in the column during the oxygen transfer tests was theoretically evaluated considering the operating conditions. Subsequently, empirical correlations were constructed using dimensionless numbers and express the oxygen transfer coefficient as a function of the superficial gas velocity and the apparent viscosity, considering its shear rate dependence. Finally, alpha factor is defined as a power law decreasing function of the apparent viscosity, for low loaded activated sludge systems.

Cette thèse s'inscrit dans le cadre d'une collaboration entre l'Ecole Nationale des TPE et les entreprises routières APPIA et EUROVIA. La société pétrolière TOTAL a également été associée à l'étude. Ce travail traite de l'analyse du comportement thermo-mécanique des enrobés bitumineux aux températures basses et intermédiaires et vise à mettre en évidence les relations entre les propriétés des liants et des enrobés. Un large travail expérimental de laboratoire a été réalisé en vue de répondre à ces deux objectifs. Il s'agit notamment de mieux cerner les critères existants de caractérisation des liants, voire d'en proposer de nouveaux, en relation avec le comportement en place des enrobés.<br /><br />Après une étude bibliographique sur la rhéologie et les propriétés thermo-mécaniques des bitumes, des mastics et des enrobés bitumineux, le travail expérimental mené aussi bien dans le domaine des petites déformations que des grandes déformations, est exposé.<br /><br />Le comportement à basse température des bitumes a été évalué avec trois tests fondamentaux largement répandus : i)l'essai de module complexe, ii)l'essai de fluage au BBR, iii)l'essai de traction directe SHRP à vitesse de déformation constante et températures constantes. En outre, un nouvel essai de fissuration, consistant en un essai de flexion trois points sur éprouvettes de bitume préentaillées, a été développé à l'ENTPE. Les paramètres de ténacité et d'énergie de rupture des bitumes à basses températures ont pu être déterminés en utilisant les hypothèses de la MLR (Mécanique Linéaire de la Rupture). <br /><br />Le comportement thermo-mécanique des enrobés bitumineux à basse température a été étudié en réalisant i)des essais de module complexe, ii)des mesures du coefficient de dilatation-contraction thermique, iii)des essais de traction à vitesses de déformation constantes, iv)ainsi que des essais de retrait thermique empêché.<br /><br />Tout d'abord, des liens pertinents entre les propriétés des liants et des enrobés, et des caractéristiques suffisamment discriminantes au regard des propriétés à basse température des enrobés ont été mis en évidence. Ensuite, l'analyse a consisté à effectuer un travail de modélisation du comportement des liants et des enrobés, en petites et grandes déformations.<br /><br />Un modèle rhéologique monodimensionnel, qui consiste en une généralisation du modèle analogique de Huet-Sayegh, a été développé dans le domaine des petites déformations. Ce modèle, appelé modèle “2S2P1D”, permet de simuler correctement à la fois le comportement visco-élastique linéaire des bitumes et celui des enrobés bitumineux. A partir de ce modèle, une transformation originale –indépendante du modèle– permettant de prédire le module complexe de l'enrobé à partir de celui du liant est proposée, puis validée.<br /><br />Enfin, la dernière partie de cette thèse est consacrée à la loi généralisée monodimensionnelle “DBN” (Di Benedetto-Neifar) à partir de laquelle un programme a été développé sur l'interface Visual Basic du logiciel Excel. Ce programme constitue un outil simple de prévision du comportement de l'enrobé bitumineux sous diverses sollicitations (mécaniques et/ou thermiques). Ce modèle rhéologique permet de faire le lien entre les petites et les grandes déformations. Des simulations d'essais de traction à vitesses de déformation constantes, ainsi que des simulations d'essais de retrait thermique, monotones ou cycliques, sont enfin présentées.

<p>Soils, in general, undergo both elastic and plastic deformations upon loading. Strain dependant anisotropic elasto-plastic models are required for realistic modeling for soil-tool mechanics that will address issues like stress history and soil anisotropy. Although several such models have been proposed, the science of coupled poro-mechanical analysis of an unsaturated soil has not been fully addressed.</p><p>Tillage tool modeling is primarily concerned with the analysis of soil deformation patterns and development of force prediction models for design optimization. Most of the models are based on quasi-static soil failure patterns that cause difficulty in accurately predicting soil-tool behaviour and soil forces for high speed operation. In recent years efforts have been made to improve the conventional analytical and experimental models by numerical approaches. Numerical simulations of soil-tool interactions using finite element modeling (FEM) and discrete element method (DEM) were mostly based on a solid mechanics approach. Due to limitations of constitutive relations, predictions of these numerical models have not been able to address tillage dynamics with high shear rates. The contribution of this research was to study the dynamics of soil-tool interaction using computational fluid dynamics (CFD) from the perspective of soil visco-plastic behavior.</p><p>A motorised soil rheometer was developed for evaluating soil visco-plastic parameters for CFD simulations. The apparatus was used to determine soil yield stress and viscosity at different soil moisture and compaction levels.</p><p>Three-dimensional CFD analyses were carried out using a commercial software CFX 4.4 to observe soil failure patterns around a tool and the pressure distribution on and around the tool. Duct flow as well as free-surface flow simulations of visco-plastic soil as a non-Newtonian Bingham material indicated soil deformation comprising of plastic flow and plug flow patterns. The soil failure front advancement demonstrated a critical speed range of 4 to 6.5 m s-1 where advancement of the failure front did not increase with speed. Soil pressure on the tool surface increased with the tool operating speed. Pressure distribution on the tool surface and draft requirement agreed well with the published literature based on experimental results and FEM analysis. The CFD approach, in its first attempt to tillage process, demonstrated its greater potential for dynamic modeling of soil-tool interaction.</p>

<p>Soils, in general, undergo both elastic and plastic deformations upon loading. Strain dependant anisotropic elasto-plastic models are required for realistic modeling for soil-tool mechanics that will address issues like stress history and soil anisotropy. Although several such models have been proposed, the science of coupled poro-mechanical analysis of an unsaturated soil has not been fully addressed.</p><p>Tillage tool modeling is primarily concerned with the analysis of soil deformation patterns and development of force prediction models for design optimization. Most of the models are based on quasi-static soil failure patterns that cause difficulty in accurately predicting soil-tool behaviour and soil forces for high speed operation. In recent years efforts have been made to improve the conventional analytical and experimental models by numerical approaches. Numerical simulations of soil-tool interactions using finite element modeling (FEM) and discrete element method (DEM) were mostly based on a solid mechanics approach. Due to limitations of constitutive relations, predictions of these numerical models have not been able to address tillage dynamics with high shear rates. The contribution of this research was to study the dynamics of soil-tool interaction using computational fluid dynamics (CFD) from the perspective of soil visco-plastic behavior.</p><p>A motorised soil rheometer was developed for evaluating soil visco-plastic parameters for CFD simulations. The apparatus was used to determine soil yield stress and viscosity at different soil moisture and compaction levels.</p><p>Three-dimensional CFD analyses were carried out using a commercial software CFX 4.4 to observe soil failure patterns around a tool and the pressure distribution on and around the tool. Duct flow as well as free-surface flow simulations of visco-plastic soil as a non-Newtonian Bingham material indicated soil deformation comprising of plastic flow and plug flow patterns. The soil failure front advancement demonstrated a critical speed range of 4 to 6.5 m s-1 where advancement of the failure front did not increase with speed. Soil pressure on the tool surface increased with the tool operating speed. Pressure distribution on the tool surface and draft requirement agreed well with the published literature based on experimental results and FEM analysis. The CFD approach, in its first attempt to tillage process, demonstrated its greater potential for dynamic modeling of soil-tool interaction.</p>

In this thesis was designed, manufactured and tested the fourth evolution of a slit-flow rheometer with another necessary parts, eg. rheometer`s holder, drive frame and important jig tools. The rheometer is able to measure rheological properties of magnetic and non-magnetic fluids at very high shear rates, which commercial rheometers can not reach. It is designed for 200 bar pressure and maximum load 15 kN. The construction of the slit-flow rheometer with it`s holder and drive frame improves user friendliness, accelerates change of the fluid sample and expands research opportunities thanks to a big space for additional adjustments. It is possible to use different length of the slit and thanks to a changeable inserts it is possible to change parameters of the slit (roughness of the walls, wall material, thickness of the slit). A part of this thesis was focused on illation of necessary equations for planning calibration measurements. Aim of these measurements is to obtain minor pressure losses dependence on Reynolds number for specific slit.

The main objectives of this research were twofold: 1). to develop advanced material characterization techniques for bitumen, mastic and mortar aiming to improve the knowledge of the behavior of asphalt concrete at micro and meso scales, and 2). to develop an efficient macro-mechanical numerical model capable of determining flexible pavement responses to traffic and environmental loads.

[pt] As propriedades reológicas na interface ar/água de modelos de surfactantes pulmonares (DPPC, DPPC:DPPG, DPPC:DPPG:Colesterol, Survanta e Curosurf) foram investigadas utilizando técnicas de cisalhamento superficiais (reometria de cisalhamento interfacial) e dilatacionais (tensiometria da gota pendente). Assim, alguns parâmetros de interesse foram obtidos para o estudo da viscoelasticidade das amostras (como viscosidade e módulos de armazenamento e perda) e as limitações das técnicas também foram analisadas. Os experimentos foram realizados de forma dinâmica, em que a faixa de frequência de interesse abrange, inclusive, a frequência respiratória de um atleta. Os resultados obtidos mostram a maior viscosidade do Survanta, frente ao Curosurf, e mostram o caráter intermediário do DPPC, que pode ser alterado pela adição de DPPG (aumentando a elasticidade) e Colesterol (aumentando a viscosidade), sugerindo que a mistura DPPC:DPPG pode ser mais adequada do que com DPPC:DPPG:COL para simular o comportamento do surfactante pulmonar. A reometria dilatacional não se mostrou aplicável ao estudo dos surfactantes, o que pode ser causado pela alta viscoelasticidade e relativa instabilidade do Survanta. / [en] The interfacial rheological properties of lung surfactants models (DPPC, DPPC:DPPG, DPPC:DPPG:Cholesterol, Survanta and Curosurf) at the air/water interface were investigated using shear (interfacial shear rheometry) and dilatacional (pendent drop tensiometry) techniques. Thus, some parameters of interest were obtained to study the viscoelasticity of the samples (such as viscosity and storage and loss modules) and the limitations of the techniques were also analyzed. The experiments were carried out dynamically, in which the interest frequency range includes the respiratory rate of an athlete. The results obtained show the higher viscosity of Survanta, compared to Curosurf, and show the intermediate character of DPPC, which can be altered by addition of DPPG (increasing the elasticity) and Cholesterol (increasing the viscosity), suggesting the DPPC:DPPG mixture may be more suitable than with DPPC:DPPG:CHOL to simulate the lung surfactant behavior. The dilatacional rheometry does not shown to be applicable for surfactants studies, which can be caused by the high viscoelasticity and relative instability of Survanta.

The application of chemical additives, known as grinding aids (GA), dates back to 1930 in the cement industry. As opposed to the cement industry, where the use of GAs is on the final processing step, it could be one of the first process steps in ore beneficiation. A few investigations addressed the GA applications in ore dressing; therefore, further studies are required to better understand the GA effects on the product properties and downstream separation processes. This thesis undertakes a comparative study on the dry grinding of magnetite and the resulting product characteristics with and without GAs. The main aim is to reduce energy consumption and to address some of the challenges associated with dry processing.  The effects of GAs on the dry batch ball milling of magnetite were examined to analyze the energy consumption (Ec), particle size distribution, flow properties, bulk properties, surface morphology, particle fineness, and surface chemistry of products. Their effects on the ground product were systematically explored by sieve analysis, powder rheology, BET surface measurements, optical microscopy analysis, and zeta potential measurements. Compared with the absence of GAs, the dry grinding efficiency of magnetite increased after using GAs; however, an optimal dosage exists based on the GA type. Among GAs which considered in this investigation (Zalta™ GR20-587 (Commercial GA) and Zalta™ VM1122 (Commercial viscosity aid) as well as sodium hydroxide), Zalta™ VM1122, a polysaccharide-based additive, was the most effective GA where by using this GA; the Ec decreased by 31.1% from 18.0 to 12.4 kWh/t. The PSD became narrower and finer (P80 decreasing from 181 to 142 µm), and the proportion of the particles (38–150 µm) increased from 52.5 to 58.3%. In general, the results reveal that at sufficient GA dosages, they reduce the average particle size, increase the specific surface area, and narrow the particle size distribution. However, an excessive amount of GAs could be detrimental to the grinding performance.  Further studies on powder rheology indicated that the used GAs resulted in improved material flowability compared to grinding without additives (in the examined dosage range). The rheology measurements by the FT4 Powder Rheometer showed strong linear correlations between basic flow energy, specific energy, and the resulting work index when GAs was considered for grinding. There was a strong correlation between the grinding parameters and flow parameters (r &gt; 0.93). These results confirmed the effect of GA on ground particles' flowability. Zalta™ VM1122 showed the best performance with 38.8% reduction of basic flow energy, 20.4 % reduction of specific energy, 24.6% reduction of aerated basic flow energy, and 38.3% reduction of aerated energy. The present investigation showed that the predominant mechanism of GAs is based on the alteration of rheological properties. Further investigation on the surface properties showed that using GAs could increase the surface roughness, which is beneficial for downstream processes such as froth flotation. Zalta™ VM1122 resulted in increased surface roughness and minimum microstructural defects from the optical microscope images. Furthermore, Zalta™ VM1122 (non-ionic) resulted in similar zeta potentials and pH values for the product compared to experiments without GA. These comparable product properties are advantageous as they minimize any potential negative effects on all possible downstream processes. / Kolarctic CBC (KO1030 SEESIMA)

[pt] Na indústria de óleo e gás, a paralisação da produção e do transporte nas linhas de fluxo causadas pela deposição de compostos orgânicos e inorgânicos rendem enormes perdas financeiras e preocupações ambientais. Um dos fatores mais comuns e críticos na deposição orgânica está relacionado com a formação de hidratos de gás, que são sólidos cristalinos de base aquosa, fisicamente semelhantes ao gelo, formados em condições de alta pressão e baixas temperaturas. Devido a esses fatos preocupantes, fenômenos relacionados aos hidratos, como formação, dissociação e formas de mitigação, vêm sendo estudados há anos por pesquisadores. Neste trabalho foram realizados experimentos para analisar a formação de hidrato de gás de etano em emulsões água em óleo, através de uma análise reológica baseada na variação de pressão, taxa de cisalhamento e fração de volume de água, e usando as geometrias vane e de cilindros concêntricos. Testes de varredura de tempo de alta pressão foram realizados, e os resultados foram apresentados através de curvas de viscosidade e pressão. A quantidade de água convertida em hidrato também foi estimada através da equação de estado e relacionada com a viscosidade das pastas de hidratos formadas. Os resultados obtidos mostram que o período de indução foi reduzido pelo aumento do subresfriamento, corte de água e taxa de cisalhamento. Quanto maior a fração de volume de água, maior o nível atingido pela viscosidade quando identificada a formação de hidratos. A viscosidade relativa, após a formação do hidrato, foi estudada. Esse conhecimento proporcionou uma compreensão mais efetiva de algumas diferenças observadas entre as duas geometrias. E para complementar o estudo, foram realizadas rampas de taxa de cisalhamento mostrando semelhanças entre os três resultados com cilindros concêntricos, mas diferenças entre os resultados com geometria vane. Ambas as geometrias, vane e cilindros concêntricos, foram consideradas adequadas para estudar a formação de hidratos e resultados qualitativos semelhantes foram obtidos. / [en] In the oil and gas industry, the stoppage of the production and transportation flowlines caused by the deposition of organic and inorganic compounds yields huge financial losses and environmental concerns. One of the most common and critical inorganic deposition is related with gas hydrates, which are crystalline water-based solids, physically similar to ice, formed in conditions of high pressure and low temperatures. Due to the worrying facts, phenomena related to hydrates, as formation, dissociation, and forms to its mitigation have been studied for years by researchers. In this work, experiments were carried out to analyze ethane gas hydrate formation in water-in-model oil emulsions, through a rheological analysis based on the variation of pressure, shear rate and water volume fraction, and using the vane and concentric cylinder geometries. High pressure time sweep tests were performed, and the results were presented through viscosity and pressure curves. The amount of water converted to hydrate was also estimated through the equation of state and related to the viscosity of the hydrate slurries formed. The results obtained showed that the induction period was reduced by increasing the subcooling, water cut, and shear rate. The higher the water volume fraction, the higher the level reached by viscosity when hydrate formation is identified. The relative viscosity after hydrate formation was studied. This knowledge provided a more effective understanding of some differences observed between the two geometries. And to complement the study, shear rate ramps were performed showing similarities between results with concentric cylinders but differences with vane. Both geometries, vane and concentric cylinders, seem to be adequate to study hydrate formation and similar qualitative results were obtained.