The main contribution of the present work is the proposition of a framework for analysis of active suspensions using the Caenorhabditis elegans nematode as the living model. To do so, five different perspectives are used: kinematics, macro-reological, numerical, theoretical and micro-reological. First, a theoretical and experimental analysis of the kinematic motion of the nematodes suspended in a biological fluid is presented. Two different populations are examined: starving and well fed nematodes. We show that the relationship between the length of an individual nematode and the wavelength of its movement is linear and can be adjusted by a theoretical prediction proposed in this work. A deep discussion on propulsive mechanics based on a scale analysis that identifies three major forces acting on an individual nematode is made. In addition, we investigated the shear viscosity of Caenorhabditis elegans suspensions. The oscillatory shear experiments revealed an anomalous viscosity behavior with the variation of the volumetric fraction of suspension, ?. The effective viscosity of the suspension decreased with increasing nematode volumetric fraction at low concentrations. Based on the experimental data, a phenomenological equation for the effective viscosity of the suspension as a function of the volumetric fraction of particles is proposed. The collective behavior of the nematodes is also observed in linear regime through the difference of normal stresses. Finally, step strain tests are conducted to obtain the relaxation times. The presence of a negative active stress due to the nematoid driving behavior persists for a period of time, leading to a negative undershoot and an oscillatory behavior in the relaxation function. In order to propose a rheological model, simplifications are made in the model and immersed boundary method simulations are conducted in a flexible filament, varying the type of movement that it performs. It is observed that the presence of asymmetries in its undulating movement generates drastic changes on its kinematic responses. A rheological model as a function of filament orientation is proposed and validated with experimental data in linear regime. After validation of the proposed constitutive equation, the model is observed under the nonlinear regime of oscillatory shear, in which the rheological characterizations are made based on existing frameworks using Lissajous-Bowditch curves and Pipkin diagrams. Finally, a protocol for analysis of suspensions in a microrheometer is presented. Particles are added and tracked as unidirectional oscillatory shear (pulsatile flow) is applied. The velocity and shear rate profiles are obtained, as well as the rheological signals equivalent to the strain rate and stress. Signal analysis tools are used and an artificial intelligence system is proposed to remove the component added to the signal by unidirectional shear, aiming to reconstruct the signal with null temporal average and allowing the application of well known rheological theories, such as the decomposition of stresses in coefficients of Chebyshev, for the calculation of viscommetric quantities of compliances and fluidities. The major contribution of the study concerns the observation, characterization, modeling and simulation of a microsized animal that moves in different fashion, depending on the environment, and the surrounding fluid. The rheological properties analyzed, simuations performed and model proposed can be used for both production of artifitial microorganisms and control of living organisms. Moreover, this combination of analyses and techniques can be used to study any type of passive and active suspension providing new and conclusive results regarding the rheological characterization and the physical behavior of the particles. / A principal contribuição do presente trabalho é a proposição de um framework de análise de suspensões ativas utilizando como modelo vivo o nematoide Caenorhabditis elegans. Para tanto, cinco perspectivas diferentes são utilizadas: cinemática, macrorreológica, numérica, teórica e microrreológica. Primeiramente, uma análise teórica e experimental do movimento cinemático das partículas ativas suspensas em um fluido biológico é apresentada. Duas populações diferentes são examinadas: na ausência de alimento e com nematoides bem alimentados. Mostramos que a relação entre o comprimento de um nematoide individual e o comprimento de onda de seu movimento é linear e pode ser ajustada por uma previsão teórica proposta neste trabalho. Uma profunda discussão sobre a mecânica de propulsão com base em uma análise de escala que identifica três forças principais que atuam em um nematoide individual é feita. Além disso, investigamos a viscosidade de cisalhamento das suspensões de Caenorhabditis elegans. Os experimentos em cisalhamento oscilatório revelaram um comportamento anômalo da viscosidade com a variação da fração volumétrica de suspensão, ?. A viscosidade efetiva da suspensão diminuiu com o aumento da fração volumétrica do nematoide para pequenas concentrações. Baseando-se nos dados experimentais, uma equação fenomenológica para a viscosidade efetiva da suspensão em função da fração volumétrica de partículas é proposta. O comportamento coletivo dos nematoides é também observado, em regime linear, pela diferença de tensões normais. Finalmente, o teste de step strain é conduzido para obter os tempos de relaxação. A presença de uma tensão ativa negativa devido ao comportamento impulsor do nematoide persiste por um certo período, levando a um undershoot negativo e a um comportamento oscilatório na função de relaxação. A fim de propor um modelo reológico, simplificações são efetuadas no modelo e simulações usando o método de fronteira imersa são conduzidas em um filamento flexível, variando o tipo de movimento que este realiza. Observa-se que a presença de assimetrias em seu movimento ondulatório gera drásticas mudanças em suas respostas cinemáticas. Um modelo reológico em função da orientação do filamento é proposto e validado com os dados experimentais em regime linear. Após a validação da equação constitutiva proposta, o modelo é observado sob o regime não-linear do cisalhamento oscilatório, no qual as caracterizações reológicas são feitas com base nos frameworks existentes, utilizando curvas de Lissajous-Bowditch e diagramas de Pipkin. Por fim, é apresentado um protocolo de análise de suspensões em um microrreômetro. Partículas são adicionadas e rastreadas à medida que um cisalhamento unidirecional (escoamento pulsátil) é aplicado. Os perfis de velocidade e taxa de cisalhamento são obtidos, assim como os sinais reológicos equivalentes à taxa de deformação e tensão. Ferramentas de análise de sinais são utilizadas e um sistema de inteligência artificial é proposto para remoção da componente constante do sinal adicionada pelo cisalhamento unidirecional, visando reconstruir o sinal com média temporal nula e possibilitando a aplicação de teorias reológicas já conhecidas, como a decomposição de tensões em coeficientes de Chebyshev para o cálculo das quantidades viscométricas de conformidade e fluidez. A principal contribuição do estudo diz respeito à observação, caracterização, modelagem e simulação de um animal microscópico que se movimenta de maneira diferente dependendo do ambiente e do fluido circundante. As propriedades reológicas analisadas, as simulações realizadas e o modelo proposto podem ser utilizados tanto para a produção de microorganismos artificiais quanto para o controle de organismos vivos. Além disso, essa combinação de análises e técnicas pode ser usada para estudo de qualquer tipo de suspensão ativa e passiva, fornecendo resultados novos e conclusivos em relação à caracterização reológica e ao comportamento físico das partículas.

L’objectif de ce travail est d’identifier les conditions et les mécanismes permettant la création d'aptitudes nouvelles ou améliorées des protéines du lactosérum à la stabilisation et texturation des mousses alimentaires.À cette fin, nous avons étudié la rhéologie interfaciale de protéines adsorbées à l’interface eau/air, les réarrangements topologiques à l’échelle de quelques films liquides, la stabilité et la rhéologie de mousses de protéines. L’étude a porté à la fois sur un mélange de protéines du lactosérum et sur sa protéine majoritaire purifiée, la ß-lactoglobuline. Pour identifier les liens avec leurs propriétés structurales et physico-chimiques, des modifications des protéines ont été générées par étuvage de poudres. Plusieurs paramètres d’étuvage ont été variés simultanément. Une large gamme de modifications structurales des protéines a été obtenue grâce au contrôle de ces paramètres. Nous avons mis en évidence que de petites modifications structurales des protéines ont des conséquences majeures sur la rhéologie interfaciale, la dynamique des réarrangements de films, la stabilité et la rhéologie des mousses.Les effets de l’étuvage des poudres sur les propriétés des mousses sont complexes, car ils dépendent étroitement de la combinaison des effets des paramètres d’étuvage, comme de la propriété de la mousse qui est mesurée. Parallèlement, l’examen de la variabilité des comportements à plusieurs échelles apporte un éclairage original sur la contribution de la rhéologie interfaciale aux propriétés de mousses de protéines. Il met notamment en évidence l’intérê / The objective of this work is to identify the conditions and mechanisms of the creation or improvement of the stability and rheology of whey proteins foams. To this aim, we studied the interfacial rheology of protein layers adsorbed at the air/water interface, the liquid films dynamics after a topological rearrangement, the stability and rheology of whey protein foams. Both a mixture of whey proteins and purified ß-lactoglobulin, used as a model protein, were studied. To study the relationships with protein structure, proteins were modified by dry-heating of whey protein powders. A wide variety of structural changes was obtained by varying simultaneously multiple dry-heating parameters.Interestingly, low-extent structural modifications have a dramatic impact on interfacial rheology, liquid film dynamics, foam stability and foam rheology. The effects of dry-heating parameters on the foam properties are complex and depend on their combination and the considered foam feature. Our original multiscale approach (interface, film dynamics and foam) sheds light on the contribution of the interfacial rheology to protein foam properties. In particular, foam dynamics have been shown to play a predominant role.

Abstract This thesis correlates rheological data into a non-linear blown film model that describes the stress and cooling-induced morphological transformations in the axial and flow profiles of the blown films. This will help to improve the physical and mechanical properties of the films in a cost effective way, which will in turn be of great benefit to the food and packaging industries. In this research, experimental and numerical studies of a blown film extrusion were carried out using two different low-density polyethylenes (LDPEs). In the experiment, the key parameters measured and analysed were molecular, rheological and crystalline properties of the LDPEs. In the numerical study, blown film simulation was carried out to determine the bubble characteristics and freeze line height (FLH). A new rheological constitutive equation was developed by combining the Hookean model with the well known Phan-Thien and Tanner (PTT) model to permit a more accurate viscoelastic behaviour of the material. For experimental verification of the simulation results, resins were processed in a blown film extrusion pilot plant using identical die temperatures and cooling rates as used in the simulation study. Molecular characteristics of both LDPEs were compared in terms of their processing benefit in the film blowing process. Based on the experimental investigation, it was found that molecular weight and its distribution, degree of long chain branching and cooling rate play an important role on melt rheology, molecular orientation, blown film processability, film crystallinity and film properties. Effect of short chain branching was found insignificant for both LDPEs. Statistical analysis was carried out using MINITAB-14 software with a confidence level of 95% to determine the effect of process variables (such as die temperature and cooling rate) on the film properties. Film properties of the LDPEs were found to vary with their molecular properties and the process variables used. Blown film model performance based on the newly established PTT-Hookean model was compared with that based on the Kelvin model. Justification of the use of PTT-Hookean model is also reported here using two different material properties. From the simulation study, it has been found that predictions of the blown film characteristics conformed very well to the experimental data of this research and previous studies using different materials and different die geometries. Long chain branching has been found as the most prominent molecular parameter for both LDPEs affecting melt rheology and hence the processability. Die temperature and cooling rate have been observed to provide similar effect on the tear strength and shrinkage properties of blown film for both LDPEs. In comparison to the Kelvin model, the PTT-Hookean model is better suited for the modelling of the film blowing process. It has also been demonstrated in this study that the PTT-Hookean model conformed well to the experimental data near the freeze line height and is suitable for materials of lower melt elasticity and relaxation time.

SOLUTION AND MELT BEHAVIOUR OF HIGH-DENSITY POLYETHYLENE - Successive Solution Fractionation mechanism - Influence of the molecular structure on the flow In the field of polyethylene characterization, one of the most challenging research topic is certainly an accurate molecular structure determination of industrial products, in terms of molar mass distribution (MMD), corresponding average-molar masses and molecular architecture (branching nature, content and heterogeneity). Solution to this long-term problem necessarily calls for a multi-disciplinary approach. Therefore, respective advantages of molecular structure characterization in solution and in the melt are exploited. In solution, chromatographic and spectroscopic methods allow determination of MMD, average branching content and intermolecular heterogeneity within their detection limits. Rheological testing in the melt could be a very powerful molecular structure investigation tool, due to its extreme sensitivity to high molar mass (MM) tailing or long chain branching (LCB) traces. But when the rheological tests results are in hand, we often still wonder what kind of molecular structure gives rise to such results. Indeed, melt signal depends on MM, MMD and LCB presence. MMD determination and LCB quantification by melt approach is impossible as long as respective effects of these molecular parameters are not clearly quantified. The general purpose of the present work is to contribute to a better molecular structure characterization of high-density polyethylene by developing, in a first time, a preparative fractionation method able to provide narrow-disperse linear and long chain branched samples, essential to separate concomitant effects of MM, MMD and LCB on rheological behaviour. Once such model fractions isolated, influence of MM and LCB on both shear and elongational flow behaviours in the melt is studied. /Dans le domaine du polyéthylène, un des sujets de recherche les plus investigués à l'heure actuelle est la détermination précise de la structure moléculaire de résines industrielles, en termes de distribution des masses molaires (MMD), de masses molaires moyennes correspondantes et d'architecture moléculaire (nature, teneur et hétérogénéité). La résolution de cette problématique nécessite une approche multi-disciplinaire, afin d' exploiter simultanément les avantages d'une caractérisation en solution et à l'état fondu. En solution, certaines méthodes chromatographiques et spectroscopiques permettent de déterminer une MMD, une teneur moyenne en branchement et leur distribution, dans leurs limites de détection. La mesure du comportement rhéologique à l'état fondu pourrait s'avérer un formidable outil de caractérisation de la structure moléculaire en raison de son extrême sensibilité à certains détails moléculaires, tels que la présence de traces de LCB ou de très hautes masses molaires (MM). Malheureusement, le signal rhéologique dépend de manière conjointe de la MM, MMD et de la présence ou non de LCB, de telle sorte que la détermination d'une MMD ou d'une teneur en LCB par cette voie est impossible aussi longtemps que les effets respectifs de ces paramètres moléculaires sur le comportement rhéologique n'ont pas été clairement et distinctement établis. L'objectif global de cette thèse est de contribuer à une meilleure caractérisation de la structure moléculaire du polyéthylène haute densité en développant, dans un premier temps, une méthode préparative de fractionnement capable de produire des échantillons, linéaires ou branchés, à MMD la plus étroite possible, indispensables en vue de séparer les effets concomitants de la MM, MMD et LCB sur le comportement rhéologique à l'état fondu. Une fois de tels objets modèles isolés, l'influence de la MM et du LCB sur le comportement rhéologique, en cisaillement et en élongation, sera étudié.

Adsorption layers of soluble surfactants enable and govern a variety of phenomena in surface and colloidal sciences, such as foams. The ability of a surfactant solution to form wet foam lamellae is governed by the surface dilatational rheology. Only systems having a non-vanishing imaginary part in their surface dilatational modulus, E, are able to form wet foams. The aim of this thesis is to illuminate the dissipative processes that give rise to the imaginary part of the modulus. <br><br> There are two controversial models discussed in the literature. The reorientation model assumes that the surfactants adsorb in two distinct states, differing in their orientation. This model is able to describe the frequency dependence of the modulus E. However, it assumes reorientation dynamics in the millisecond time regime. In order to assess this model, we designed a SHG pump-probe experiment that addresses the orientation dynamics. Results obtained reveal that the orientation dynamics occur in the picosecond time regime, being in strong contradiction with the two states model. <br><br> The second model regards the interface as an interphase. The adsorption layer consists of a topmost monolayer and an adjacent sublayer. The dissipative process is due to the molecular exchange between both layers. The assessment of this model required the design of an experiment that discriminates between the surface compositional term and the sublayer contribution. Such an experiment has been successfully designed and results on elastic and viscoelastic surfactant provided evidence for the correctness of the model. <br><br> Because of its inherent surface specificity, surface SHG is a powerful analytical tool that can be used to gain information on molecular dynamics and reorganization of soluble surfactants. They are central elements of both experiments. However, they impose several structural elements of the model system. During the course of this thesis, a proper model system has been identified and characterized. The combination of several linear and nonlinear optical techniques, allowed for a detailed picture of the interfacial architecture of these surfactants. / Amphiphile vereinen zwei gegensätzliche Strukturelemente in einem Molekül, eine hydrophile Kopfgruppe und ein hydrophobe, meist aliphatische Kette. Aufgrund der molekularen Asymmetrie erfolgt eine spontane Adsorption an der Wasser-Luft Grenzfläche. Die Adsorptionsschicht verändert die makroskopischen Eigenschaften des Materials, z.B. die Grenzflächenspannung wird erniedrigt. Amphiphile sind zentrale Bauelemente der Kolloid- und Grenzflächenforschung, die Phänomene, wie Schäume ermöglichen. <br><br> Eine Schaumlamelle besteht aus einem dünnen Wasserfilm, der durch zwei Adsorptionsschichten stabilisiert wird. Die Stabilität der Lamelle wird durch die Grenzflächenrheologie entscheidend geprägt. Die wesentliche makroskopische Größe in diesem Zusammenhang ist das so genannte Grenzflächendilatationsmodul E. Es beschreibt die Fähigkeit des Systems die Gleichgewichtsgrenzflächenspannung nach einer Expansion oder Dilatation der Adsorptionschicht wieder herzustellen. Das Modul E ist eine komplexe Größe, in dem der Imaginärteil direkt mit der Schaumstabilität korreliert. <br><br> Diese Arbeit widmet sich der Grenzflächenrheologie. In der Literatur werden zwei kontroverse Modelle zur Interpretation dieser Größe diskutiert. Diese Modelle werden experimentell in dieser Arbeit überprüft. Dies erfordert die Entwicklung neuer experimenteller Aufbauten basierend auf nichtlinearen, optischen Techniken. Mit diesen Experimenten konnte eines der Modelle bestätigt werden.

In this study, a mathematical model is developed for investigating the discrete sound propagation in viscoelastic medium to identify its viscoelastic properties. The outcome of the model suggests that pulse repetition frequency is a very important parameter for the determination of relaxation time. Adjusting the order of magnitude of the pulse repetition frequency, the corresponding relaxation time which has similar magnitude with pulse repetition frequency is filtered while the others in the spectrum are discarded. Discrete relaxation spectrum can be obtained by changing the magnitude of the pulse repetition frequency. Therefore, the model enables to characterize the relaxation times by ultrasonic measurements.

Thermal recovery methods are frequently used to enhance the production of heavy crude oils. Steam-based processes are the most economically popular and effective methods for heavy oil recovery for several decades. In general, there are various mechanisms over steam injection to enhance and have additional oil recovery. However, among these mechanisms, steam distillation plays pivotal role in the recovery of crude oil during thermal recovery process. In this study, an experimental investigation was carried out to investigate the role of various minerals present in both sandstone and carbonate formations as well as the effect of steam temperature on steam distillation process. Two different types of dead-heavy crude oils were tested in a batch autoclave reactor with 30 % water and the content of the reactor (crude oil, 10 % rock and mineral). The results were compared as the changes in the density, viscosity and chemical composition (SARA and TPH analyses) of heavy crude oil. Five different mineral types (bentonite, sepiolite, kaolinite, illite and zeolite) were added into the original crude oil and reservoir rocks to observe their effects on the rheological and compositional changes during steam distillation process. Analysis of the results of experiments with Camurlu and Bati Raman heavy crude oils in the presence of different minerals such as Bentonite, Zeolite, Illite, Sepiolite, and Kaolinite in both sandstone and limestone reservoir rocks indicate that steam distillation produces light end condensates which can be considered as solvent or condensate bank during steam flooding operation. It was also illustrated that minerals in reservoir formations perform the function of producing distilled light oil compounds, resulting in enhancement of heavy crude oils recovery in steam flooding. Measurements showed that the remaining oil after steam distillation has higher viscosity and density. On the other hand, the effect of steam distillation is more pronounced in limestone reservoirs compared to sandstone reservoirs for the given heavy crude oil and steam temperature. Among the five different minerals tested, kaolinite found to be the most effective mineral in terms of steam distillation.

The complex interaction between cement and chemical/mineral admixtures in concrete mixtures sometimes leads to unpredictable concrete performance in the field which is generally defined as concrete incompatibilities. Cement paste rheology measurements instead of traditional workability tests (i.e., slump cone test) can have great potential in detecting those incompatibilities in concrete before the concrete is placed, which can, in turn, avoid related workability problems and setting time as well as heat evolution abnormalities. The objectives of the present study were to examine the applicability of the dynamic shear rheometer (DSR) to measure cement paste rheology, and to identify cement and mineral/chemical admixture incompatibilities, based on the determined rheological parameters. The DSR was modified and optimized for cement paste rheology measurements. Two different modes of operations (i.e., static and dynamic methods) with the modified DSR were investigated to measure representative rheological parameters as well as to identify cement and chemical/mineral admixture incompatibility. The conventional plastic viscosity and yield stress are measured in static mode and storage modulus curve, as a function of time, is measured in dynamic mode. The rate of change of plastic viscosity (RPV) as another static rheological parameter and the modeled magnitude parameter ?, from the dynamic rheological method, showed great potentialities as acceptance criteria to identify incompatible mixtures. The heat of hydration data from isothermal conduction calorimeter tests and setting time results for the studied mixtures have strongly supported the rheology based observations as supporting tools. Based on the main tests results, the acceptance criteria were set up using the rheological parameters in accordance with heat of hydration data. This will ultimately help material suppliers, concrete producers, and other users to detect problematic combinations of concrete ingredients before a given concrete mixture is placed.

The recovery characteristics of Bolu-Himmetoglu, Bolu-Hatildag, K&uuml / tahya- Seyit&ouml / mer, and Nigde-Ulukisla oil shale samples and Bati Raman, &Ccedil / amurlu, and Garzan crude oil samples were tested experimentally using retort and microwave heating techniques. Many parameters like heating time, porosity, water saturation were studied. To enhance the efficiency of the processes three different iron powders (i.e. / Fe, Fe2O3, and FeCl3) were added to the samples and the doses of the iron powders were optimized. While crude oil viscosities were measured to explain the fluid rheologies, since it is impossible to measure the shale oil viscosity at the laboratory conditions due to its very high viscosity, shale oil viscosities were obtained numerically by using the electrical heating option of a reservoir simulator (CMG, STARS 2007) by matching between the laboratory and numerical oil production and temperature distribution results. Then the field scale simulations for retorting of oil shale and crude oil fields were conducted. Since the microwave heating cannot be simulated by CMG, STARS, microwave heating was modeled analytically. In order to explain the feasibility of heating processes, an economic evaluation was carried out. The experimental, numerical, and analytical results show that field scale oil recovery from oil shales and heavy crude oils by electrical and electromagnetic heating could be economically viable. While microwave heating is advantageous from an operational point of view, retorting is advantageous if the technically feasibility of the study is considered.

Aircraft are not allowed to take off prior to cleaning of snow and ice deposits that form on their surfaces under winter conditions to refrain from compromising flight safety. Water based solutions containing mainly ethylene or propylene glycol, or both, are employed either to remove the snow/ice layers or to provide protection against deposition of these layers. The first group of solutions, i.e. de-icing fluids, are Newtonian and have generally low viscosity so that right after their application they fall off the aircraft surfaces, providing little or no further protection against precipitation. Therefore, various anti-icing solutions have then been developed to provide the prolonged protection due to their non-Newtonian and high viscosity characteristics. Although the appropriate ranges of viscosity and surface tension have been determined in a number of studies, actual compositions of these solutions are proprietary. The main objective of this study is to determine the basic interactions between the chemical species in de/anti-icing fluids and their effects on the physical properties of the solutions, especially viscosity, surface tension,freezing point and corrosive effect which enable the design of the de/anti icing fluid composition. A number of polymers and surfactants were dissolved in water-glycol solutions and used in different compositions to get the desired viscosity and surface properties. The dependence of viscosity on polymer concentration, pH of the solutions, glycol content, surfactant concentration, temperature and shear rate were investigated and reported in detail. Among various chemicals, slightly crosslinked and hydrophobically modified polyacrylic acid was utilized as a thickener, sodium oleate and tributyl amine were used as surface agents in the de/anti-icing solutions whose physical properties satisfied the desired requirements. In addition to the studies about de/anti icing solutions, synthesis of a new polymer namely poly (DADMAC-co-vinyl pyyrolidone) was made and its characterization and performance tests were performed. High swelling ratios (up to 360) were attained with 0.5 % crosslinker in 2-3 minutes. Moreover, swellings of the gels were demonstrated to be independent of pH. It was also thought that such a copolymer having anti-bacterial effect induced by DADMAC (Diallyldimethyl ammonium chloride) segments and biocompatability of NVP (N-vinyl pyyrolidone) component would be of interest in biorelated areas.