Dissertations / Theses on the topic 'Dynamic shear rheology'

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1

Romo-Uribe, Angel. "Main-chain thermotropic liquid crystalline polymers under shear : a dynamic scattering study." Thesis, University of Cambridge, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243155.

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2

Pieri, Marco. "Shear deformation of calcite rocks : rheology and microfabric evolution of Carrara marble under dynamic recrystallization during torsion experiments /." Zürich : ETH, 1999. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=13220.

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3

Střasáková, Monika. "Stárnutí asfaltových pojiv." Master's thesis, Vysoké učení technické v Brně. Fakulta stavební, 2016. http://www.nusl.cz/ntk/nusl-240117.

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The theoretical part of this thesis describes the rheology of bituminous binders, aging of asphalt binders and laboratory methods simulating short and long term aging. The following describes an empirical tests (needle penetration, softening point ring ball method) and functional tests (complex shear modulus and phase angle, dynamic viscosity), which are performed in the dynamic shear rheometer. At the end of this section, laboratory aging of bituminous binders using method RTFOT and method RTFOT + PAV is described in more detail. In the practical part of this thesis, the results of all tests performed on the binders aged using RTFOT + PAV are introduced and compared with results of properties of non-aged binders and binders aged by 3xRTFOT.
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4

Pěnčík, Michal. "Reologické vlastnosti asfaltových pojiv." Master's thesis, Vysoké učení technické v Brně. Fakulta stavební, 2015. http://www.nusl.cz/ntk/nusl-227653.

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The Diploma thesis is focused on rheological properties of bituminous binders and mixtures. Above all, it describes the changes of these properties of samples of bituminous binders and mixtures. Those were brought by the process of laboratory aging, since it simulates the changes occurring in the in the real-life conditions. The theoretical part depicts the field of rheology and methods utilized for simulating the ageing of binders and mixtures. The practical part describes the process of preparation of samples and its testing. Firstly, the ageing of bituminous mixture by the means of BSA method (Braunschweiger Alterung) took place, which was followed by preparing the solids for testing the modulus of stiffness and main testing. The rest of the mixture was used for extracting the binder. Tests with the binder were focused on the usage of dynamic shear rheometer (complex shear modulus, dynamic viscosity). The last part of the work is dedicated to the comparison of the outcomes of testing.
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5

Tsamados, Michel. "Mechanical response of glassy materials : theory and simulation." Phd thesis, Université Claude Bernard - Lyon I, 2009. http://tel.archives-ouvertes.fr/tel-00466081.

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Il est bien établi que les propriétés mécaniques et rhéologiques d'une large classe de matériaux vitreux amorphes met en jeu - contrairement aux dislocations dans les cristaux - des rearrangements structuraux localisés formant par un processus de cascade des bandes de cisaillements. Cette localisation de la déformation est observée dans divers systèmes vitreux ainsi que dans des simulations numériques. Cette réponse mécanique complexe reste mal comprise à une échelle microscopique et il n'est pas clair si l'écoulement plastique peut être associé à une origine structurale locale ou à des processus purement dynamiques.Dans cette thèse nous envisageons ces problématiques à l'aide de simulations atomiques athermales sur un système Lennard-Jones modèle. Nous calculons le tenseur élastique moyenné localement sur une échelle nanométrique. A cette échelle, le verre est assimilable à un matériau composite comprenant un échafaudage rigide et des zones fragiles. L'étude détaillée de la déformation plastique à différents taux de cisaillement met en évidence divers régimes d'écoulement. En dessous d'un taux de cisaillement critique dépendant de la taille du système, la réponse mécanique atteind une limite quasistatique (effets de taille fini, cascades d'événements plastiques, contrainte seuil) alors que pour des taux de cisaillement plus importants les propriétés rhéologiques sont fixées par le taux de cisaillement imposé. Dans ce régime nous mettons en évidence la croissance d'une longueur de coopérativité dynamique et discutons de sa dépendance avec le taux de cisaillements.
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6

Ali, Nabil. "RhéoSpeckle : un nouvel outil d’étude du comportement multi-échelle des matériaux hétérogènes." Thesis, Université Grenoble Alpes (ComUE), 2016. http://www.theses.fr/2016GREAI013/document.

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Ce travail de thèse cherche à mieux caractériser le comportement des matériaux hétérogènes sous cisaillement avec une approche multi-échelles (macro-méso-microscopique).Cela est rendu possible en développant un montage innovant qui couple un rhéomètre à un système d’imagerie de speckle résolue spatialement et temporellement (RheoSpeckle). Nous montrons la validation de notre expérience en l’appliquant sur deux matériaux parfaits : un solide et un liquide. Sur le solide, on mesure le champ de déplacement sur les images de speckle avec une résolution meilleure que 1 µm. Puis on prouve l’élasticité du matériau à l’échelle microscopique. Sur le liquide, la taille des nanoparticules est déterminée avec un excellent accord avec la spécification du fabriquant. Le champ de vitesse dans l’entrefer du Couette est calculé avec une bonne précision sur un temps inférieur à 1 s et avec une résolution spatiale de 100 µm sur 5mm. La dynamique microscopique d’une solution brownienne est étudiée et l’influence du cisaillement sur la décorrélation est déterminée. Nous montrons les capacités de notre expérience à étudier des matériaux hétérogènes en l’appliquant sur une solution concentrée de micelles géantes. La rhéologie linéaire est étudiée en rhéometrie classique mais aussi en utilisant l’imagerie du speckle. La rhéologie non linéaire de ce matériau est déterminé en rhéometrie (macro) mais aussi en calculant le champ de vitesse et l’intensité des images de speckle (méso) ou on caractérise les bandes de cisaillement qui se forment à partir d’un cisaillement critique. En fin la relaxation spatio-temporelle des bandes de cisaillement (micro) est caractérisée. On observe pour la première fois l’existence de deux temps de relaxation après l’arrêt du cisaillement et que la relaxation des bandes est relativement lente
This work tries to better characterize the behavior of homogeneous and heterogeneous materials under shear with a multi-scale approach (macro-meso-micro-scopic). To do that, we have developed an innovative setup by coupling a rheometer to a speckle imaging geometry witch is spatially and temporally resolved (RheoSpeckle). We validate our experience using two perfect materials: a solid and a pure viscous fluid. On a solid sample, we calculate the displacement field on the speckle images with a resolution better than 1 µm. we demonstrate than, the microscopic elasticity of this material. On a pure viscous fluid, we measured the nanoparticle’s size with excellent accuracy. When a constant shear rate is applied, the velocity profile is measured with a time less than 1 s with a spatial resolution of 100 µm over 5 mm. The microscopic dynamic of a Brownian solution under shear is probed and the shear induced on the decorrelation of the intensity correlation function is studied. We show the capabilities of our experience using a concentrated solution of wormlike micelles. The linear rheology is studied using rheometric measurements and our speckle imaging system. Nonlinear rheology is studied using rheometric measurements (macro), but also by calculating the velocity filed and the intensity of speckle images (meso). With mesocopics measurements, the formation of shear banding is proved and characterized. Finally, the spatio-temporal relaxation (micro) of shear bands of this material is studied. We show for the first time the existence of two relaxations times after shear and that the relaxation of bands is relatively slow
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7

Isreb, Mohammad. "Thermal and rheological approaches for the systematic enhancement of pharmaceutical polymeric coating formulations : effects of additives on glass transition temperature, dynamic mechanical properties and coating performance in aqueous and solvent-free coating process using DSC, shear rheometry, dissolution, light profilometry and dynamic mechanical analysis." Thesis, University of Bradford, 2011. http://hdl.handle.net/10454/5527.

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Additives, incorporated in film coating formulations, and their process parameters are generally selected using a trial-and-error approach. However, coating problems and defects, especially those associated with aqueous coating systems, indicate the necessity of embracing a quality-by-design approach to identify the optimum coating parameters. In this study, the feasibility of using thermal and rheological measurements to help evaluate and design novel coating formulations has been investigated. Hydroxypropyl methylcellulose acetate succinate (HPMCAS), an enteric coating polymer, was used as the film forming polymer. Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), and Parallel Plate Shear Rheometery (PPSR) were used to evaluate the effect of different plasticisers on the performance of HPMCAS. The results illustrate that, for identical formulations, the DSC and DMA methods yielded up to 40% differences in glass transition temperature (Tg) values. Moreover, Tg measured using loss modulus signals were always 20-30 oC less than those measured using tan delta results in DMA testing. Absolute and relative Tg values can significantly vary depending on the geometry of the samples, clamp size, temperature ramping rate and the frequency of the oscillations. Complex viscosity data for different formulations demonstrated a variable shear thinning behaviour and a Tg independent ranking. It is, therefore, insufficient to rely purely on Tg values to determine the relative performance of additives. In addition, complex viscosity results, obtained using both the DMA and PPSR techniques at similar temperatures, are shown to be comparable. The results from both techniques were therefore used to produce continuous master curves for the HPMCAS formulations. Additionally, step strain tests showed that HPMCAS chains do not fully III disentangle after 105 seconds as predicted by the Maxwell model. Finally, in situ aqueous-based coating experiments proved that mixtures of triethyl acetyl citrate and acetylated monoglyceride (TEAC/AMG), even without cooling of the suspension, do not cause blocking of the spray nozzle whereas triethyl citrate (TEC) based formulae did. TEAC (alone or in a combination with AMG) exhibits superior wettability to HPMCAS than TEC/AMG formulations and can be used to enhance the efficiency and film quality of the dry coating process.
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8

Ali, Mahdi. "Study of the bitumen aging effects on the rheological properties and fatigue behavior." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2018. http://amslaurea.unibo.it/16255/.

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A study of bitumen aging effects on the rheological properties and fatigue behavior is carried out on five polymer modified bitumen provided by an oil company. Dynamic Shear Rheometer (DSR), is used to perform advanced experimental investigation. It allows practicing frequency sweep tests, fatigue tests and time sweep tests. Polymer modified bitumen with different percentage of SBS with or without the presence of crumb rubber are tested before and after short and long aging processes. Master curves were generated based on frequency sweep tests data, they are studied, and a comparison was conducted between each bitumen before and after aging. In this thesis, the DSR is presented, as well as the testing procedure and the tested materials. A fatigue life analysis of the results, based on the use of two different criteria, the first criterion is classically used: it consists in defining the failure as a 50% loss of the initial stiffness. The other criteria based on dissipated energy data. This thesis provides results which show the effects of several factors on fatigue and healing response such as bitumen type, ageing, the presence of rubber and polymer modification.
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9

Bos�ko, Jaroslaw Tomasz, and jbosko@unimelb edu au. "Molecular simulation of dendrimers under shear." Swinburne University of Technology. Centre for Molecular Simulation, 2005. http://adt.lib.swin.edu.au./public/adt-VSWT20050804.141034.

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In this work flow properties of dendrimers are studied with the aid of molecular simulations. For the first time the results of the nonequilibrium molecular dynamics simulations of the dendrimers in the melt are reported. Molecules are modelled at the coarse-grained level using the bead-spring model. The objective of this research is to analyse the influence of the molecular topology in the macroscopic flow behaviour of the melts. Systems of dendrimers of generations 1 to 4 undergoing planar shear are compared to the melts composed of linear chain polymers. The internal structure and shape of dendrimers is extensively analysed. The response of the molecules to the shearing in the form of stretching and alignment is studied. The correlation between the onset of shear thinning and the onset of deformation of molecules is observed. The changes in the fractal dimensionality of dendrimers due to shearing are also analysed. Dendrimers, due to their highly branched structure and compact globular conformations in the melt, are found to behave differently when sheared, compared to traditional linear polymers. Unlike linear polymers, they do not undergo transition form the Rouse to the reptation regimes. This effect is explained in terms of the suppressed entanglement between molecules. Moreover, dendrimers when compared to linear chain systems exhibit lower Newtonian viscosity, onset of the shear thinning at higher strain rates, and less pronounced shear thinning in the non-Newtonian regime. They can be used as rheology modifiers, as it is shown in the preliminary results obtained from the simulations of the dendrimers-linear polymer blends. In agreement with other theoretical and experimental studies, dendrimers in the melt are found to have compact space-filling structure with terminal groups distributed throughout the interior of the molecule. Suggestions for the further study of dendrimers via molecular simulations are made.
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10

Madraki, Fatemeh. "Shear Thickening in Non-Brownian Suspensions." Ohio University / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=ohiou1584354185678102.

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11

Musil, Vladimír. "Relaxace smykového napětí asfaltových pojiv v DSR." Master's thesis, Vysoké učení technické v Brně. Fakulta stavební, 2015. http://www.nusl.cz/ntk/nusl-227690.

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The thesis describes the relaxation properties of bituminous binders determined in dynamic shear rheometer (DSR). Paving bitumen, polymer modified bitumen (PMB) and crumb rubber modified bitumen (CRmB) were chosen for comparison. In order to describe the effects of ageing on asphalt binders relaxation properties, the laboratory simulation of ageing using RTFOT and 3xRTFOT method was performed. For each binder were simultaneously conducted tests of needle penetration, softening point and elastic recovery. Selected bitumens were used for the production of asphalt mixtures. The low-temperature properties tests (TSRST) were performed for these mixtures, when the results were compared to the relaxation properties of binders determined in the DSR.
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12

Hotař, Petr. "Reologické vlastnosti asfaltových pojiv." Master's thesis, Vysoké učení technické v Brně. Fakulta stavební, 2014. http://www.nusl.cz/ntk/nusl-226951.

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The comparison of rheological properties (complex shear modulus and phase angle and dynamic viscosity) of four paving bitumens and two polymer modified bitumens is performed in this diploma thesis. Furthermore, the empirical tests (needle penetration and softening point) were determined on these binders. Effect of asphalt binders aging was modeled using RTFOT test and modified RTFOT test (3 x RTFOT).
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13

Snook, Braden. "The dynamics of the microstructure and the rheology in suspensions of rigid particles." Thesis, Aix-Marseille, 2015. http://www.theses.fr/2015AIXM4700.

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Des méthodes numériques et expérimentales ont été utilisées pour identifier la relation entre les propriétés macroscopiques et la microstructure d'une suspension contenant soit des sphères soit des fibres rigides. Pour les fibres, les résultats en utilisant un modèle numérique original indiquent que les contacts sont dominants dans la prédiction de la dynamique de la microstructure. Les résultats montrent en outre que les contacts doivent être inclus dans le calcul des contraintes afin de prédire avec précision les différences de contraintes normales. Des expériences ont été effectués pour mesurer les différences de contraintes normales et ont sont en accord avec les prédictions numériques. Cela valide le modèle développé et ses résultats. Les écarts avec les travaux antérieurs dans la littérature ont été examinées. Le temps nécessaire pour atteindre l'état d'équilibre et l'influence de confinement de la géométrie expérimentale peuvent être la source de ces différences. Pour les sphères, une expérience a été construite pour étudier la dynamique de la migration de particules dans un écoulement de Poiseuille. Nous avons mesuré la fraction volumique de particules avec une grande résolution ainsi que les distribution de vitesse. Les résultats dans le régime stationnaire de migration finale ont été jugés en excellent accord avec les précédentes simulations discrètes et les expériences dans des géométries et concentrations. La dynamique a été comparée à le modèle de bilan de suspension ('Suspension Balance Model'). L'accord avec ce modèle n'est bon qu'à grande fraction volumique. Des développements supplémentaires concernant la rhéologie utilisés dans le SBM sont nécessaires
Numerical and experimental methods were used to reveal the complex relationship between the macroscopic properties and the microstructure of a suspension where either spheres or rigid fibers were considered. For fibers, results using a newly developed numerical model indicate that contacts are dominant in predicting the dynamics of the microstructure. The results show contacts must be included in calculating the stress in order to accurately predict the normal stress differences as well. Experiments measuring the normal stress differences were performed and were found to be in agreement with the numerical predictions, validating the model and its results. Discrepancies with previous work in the literature were examined. The long time required to reach steady state and the influence of confinement from the experimental geometry were found to be the source of these differences. For spheres, an experiment was built to study the dynamics of particle migration in parabolic flow. High-resolution particle volume fraction and velocity distribution measurements were made. Steady state results were found to be in excellent agreement with previous discrete element simulations and experiments at similar geometries and volume fractions. Dynamic results were compared to the suspension balance model (SBM). Excellent agreement with the SBM was exhibited only at the highest bulk particle volume fraction. Accordingly, additional development of the rheology used in the SBM is required to understand the role of the bulk volume fraction on its predictions. The results from this experiment will greatly aid this endeavor by providing the experimental data required for validation
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Sridharan, Harini. "COUPLED DYNAMICS OF HEAT TRANSFER AND FLUID FLOW IN SHEAR RHEOMETRY." University of Akron / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=akron1597346164780318.

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15

Braak, Etienne. "Aération pour le décolmatage dans les bioréacteurs à membranes immergées pour le traitement des eaux usées : impact sur le milieu biologique et la filtration." Phd thesis, Toulouse, INPT, 2012. http://oatao.univ-toulouse.fr/8859/1/braak.pdf.

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Cette étude présente les travaux réalisés pour comprendre l'effet de l'aération sur le milieu biologique et sur la filtration dans les bioréacteurs à membranes immergées pour une gamme de paramètres opératoires proche de celles utilisées sur stations réelles. Notre démarche fait le lien entre paramètres opératoires (débit d'aération), hydrodynamique à l'échelle macroscopique (tailles et vitesses de bulles), hydrodynamique à l'échelle locale (contraintes de cisaillement) et propriétés du milieu biologique (taille de flocs et substances polymériques extracellulaires solubles). De moins bonnes performances de filtration à plus forte aération pourraient être expliquées par une plus grande déstructuration des boues sur le court terme. Par ailleurs tout effet d'évolution des boues sur le long terme en fonction des conditions d'aération a été écarté.
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16

Huang, Chien-Cheng. "Statics, dynamics, and rheological properties of micellar solutions by computer simulation." Thesis, Universite Libre de Bruxelles, 2007. http://www.theses.fr/2007METZ022S/document.

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Les propriétés statiques, dynamiques, rhéologiques et la cinétique de scissions et recombinaisons de micelles linéaires auto-assemblées sont étudiées à l'équilibre et sous-écoulement par simulations sur ordinateur, en utilisant un modèle mésoscopique nouveau. Nous représentons les micelles comme des séquences linéaires de billes browniennes dont l'évolution spatio-temporelle est gouvernée par la dynamique de Langevin. Un algorithme de Monte-Carlo contrôle l'ouverture des liens ou la fusion de deux chaînes par les bouts. Un paramètre cinétique o, qui modélise l'effet d'une barrière le long d'un chemin de réaction, est introduit dans notre modèle. A l'équilibre, nous nous concentrons sur les mécanismes de scission/recombinaison aux temps long et court. Nos résultats montrent que pour les temps plus grands que le temps de vie d'une chaîne moyenne, la cinétique est en accord avec le modèle champ-moyen de Cates. L'étude de fonctions de relaxation macroscopique confirme que nos constantes cinétiques effectives obtenues aux temps longs sont pertinentes pour ces relaxations. Pour la situation hors équilibre, nous étudions les effets du couplage entre un écoulement de cisaillement et la cinétique de scission et recombinaison sur les propriétés structurales et rhéologiques du système micellaire. Nous nous plaçons dans un régime semi-dilué et dynamiquement 'unentangled'. Le paramètre o est choisi de façon à ce que la durée de vie d'une chaîne moyenne soit plus courte que son temps de relaxation de Rouse le plus long. Nos analyses font apparaître une longueur dynamique A, le fiagrnent de chaîne dont la durée de vie TA est égale à son temps de Rouse. Nous trouvons que les propriétés telles que la rhéo-fluidification, l'orientation des chaînes et l'étirement des liens sont des fonctions du taux de cisaillement réduit PA= YT* , alors que la longueur moyenne des micelles est une fonction décroissante du taux de cisaillement, indépendamment de la barrière du processus scission/recombinaison
Statics, Dynamics, and Rheological properties of Micellar solutions by Computer Simulation Statics, dynamics, rheology and scission-recombination kinetics of self-assembling linear micelles are investigated at equlibrium state and under shear flow by computer simulations using a newly proposed mesoscopic model. We model the micelles as linear sequences of Brownian beads whose space-time evolution is governed by Langevin dynamics. A Monte Carlo algorithm controls the opening of a bond or the chain-end fusion. A kinetic parameter o, modelling the effect of a potential barrier along a kinetic path, is introduced in our model. For equilibrium state we focus on the analysis of short and long time behaviors of the scission and recombination mechanisms. Our results show that at time scales larger than the life time of the average chain length, the kinetics is in agreement with the mean-field kinetics model of Cates. By studying macroscopic relaxation phenomena such as the average micelle length evolution after a T-jump, the monomer diffusion, and the zero shear relaxation function, we confirm that the effective kinetic constants found are indeed the relevant parameters when macroscopic relaxation is coupled to the kinetics of micelles. For the non-equilibrium situation, we study the coupled effects of the shear flow and the scissionrecombination kinetics, on the structural and rheological properties of this micellar system. Our study is performed in semi-dilute and dynamically unentangled regime conditions. The explored parameter o range is chosen in order for the life time of the average size chain to remain shorter than its intrinsic (Rouse) longest relaxation time. Central to our analysis is the concept of dynamical unit of size A, the chain fiagrnent for which the life time TA and the Rouse time are equal. Shear thinning, chain orientation and bond stretching are found to depend upon the reduced shear rate P1\=y~A while the average micelle size is found to decrease with increasing shear rate, independently of the height of the barrier of the scission-recombination process
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Miller, Erik. "The dynamics and rheology of shear -banding wormlike micelles and other non -Newtonian fluids." 2007. https://scholarworks.umass.edu/dissertations/AAI3275776.

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Non-Newtonian fluids play an important role in our daily world. While the nomenclature may be unfamiliar to most people, these fluids, also referred to as “viscoelastic”, comprise a class of materials found in a wide variety of items ranging from food, to cosmetic products, to the plastic containers they are all contained within. The design and tunability of non-Newtonian fluids is only possible through an understanding of their complex dynamics and rheology. Industrial plastics are formed into a final product through a host of fabrication techniques in which the material quality and finish is important. Sharkskin, observed in the extrusion of commercial polymer melts, is an instability that has adverse effects on surface finish. We have performed experiments towards the goal of not simply eliminating, but controlling the instability. By focusing on the rheology of polymer melts, our results have shown that the instability is caused purely by specific thermal conditions within the extrusion die, which can be both characterized and precisely controlled. Another important class of viscoelastic fluids is solutions of surfactants. Their unique molecular amphiphilic chemistry allows them to form long wormlike micellar structures, which behave like a “living polymer”. These fluids are known to exhibit a flow phenomenon called “shear-banding”; above a critical stress, they enter a non-linear regime characterized by a stress plateau in which the fluid forms distinct bands of varying shear-rate. By measuring velocity profiles using particle-image velocimetry (PIV) and stress-fields using a flow-induced birefringence (FIB) method, both at very high resolution, we have uncovered some interesting rheological behavior underlying the shear-banding kinematics. We have also performed extensional rheology experiments to supplement the shear results. Our study focused on obtaining detailed experimental data to provide insight into complex flow behavior and drive the development of constitutive models to predict shear-banding and other phenomena. This experimental methodology and the resultant models provide a highly detailed framework with which it is possible to design viscoelastic fluids having specific rheological properties for applications as intricate as tissue-engineered biomaterials.
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18

Zausch, Jochen [Verfasser]. "Dynamics, rheology and critical properties of colloidal fluid mixtures : molecular dynamics studies in Equilibrium and under shear / vorgelegt von Jochen Zausch." 2009. http://d-nb.info/993625959/34.

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19

Schneider, Ludwig. "Rheology and Structure Formation in Complex Polymer Melts." Doctoral thesis, 2019. http://hdl.handle.net/11858/00-1735-0000-002E-E60C-C.

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20

Negi, Ajay Singh. "Soft Matter Under Electric Field And Shear." Thesis, 2008. http://hdl.handle.net/2005/717.

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‘Soft condensed matter’ is a newly-emerged sub-discipline of physics concerned with the study of systems that are mechanically soft such as colloids, emulsions, surfactants, polymers, liquid crystals, granular media and various biomaterials including DNA and proteins. These materials display a broad range of interesting microstructures and phase behaviours and have a myriad of applications in the materials, food, paint and cosmetic industries as well as medical technologies. Soft condensed matter physics presents new opportunities and challenges for the development of new ideas and concepts in experimental and theoretical physics alike. Because the field overlaps with many different disciplines, the study of soft matter also offers promising developments to other fields of science including chemistry, chemical engineering, materials science, biology, and environmental science. The behaviour of these systems is dominated by one simple fact: they contain mesoscopic structures in the size range 10 nm to 1 µm that are held together by weak entropic forces. The elastic constants of these materials are 109 times smaller than the conventional atomic materials and hence are easily deformable by external stresses, electric or magnetic fields, or even by thermal fluctuations. We have studied two important classes of soft matter systems in this thesis -colloidal suspensions and surfactant systems. The thesis is divided into two main themes: (a) Effects of electric field on the colloidal suspensions, and (b) Effects of shear on surfactant solutions. Motions of colloidal particles under the influence of applied electric field were observed under a microscope and were studied using image analysis and particle tracking. We have also used tracking of thermal fluctuations of colloidal particles embedded in surfactant gels to study microrheology of surfactant solutions. Linear and non-linear rheology of aqueous solutions of cationic cetyltrimethyl ammonium bromide (CTAB) and anionic sodium-3-hydroxynapthalene-2-carboxylate (SHNC) were studied using bulk rheology in a commercial rheometer. Rheological studies of an anionic surfactant sodium dodecyl sulphate (SDS) in the presence of strongly binding counterion p-toluidine hydrochloride (PTHC) has also been done. Chapter 1 starts with a general introduction to soft condensed matter systems and then we proceed to describe two specific class of soft condensed materials which we have studied in this thesis -colloidal suspensions and surfactant/water systems. After describing different types of colloids, we discuss why colloids are suitable as model systems in condensed matter physics. This is followed by a discussion on the chemical structure, phase behaviour and self assembling properties of surfactant molecules in water. We then discuss the inter-macromolecular forces such as van der Waals interaction, the screened Coulomb repulsion, hydrogen bond, hydrophobic and hydration forces and steric repulsion which are the major players in the interaction in soft condensed matter systems. The systems that have been the subject of our experimental studies, viz. polystyrene colloidal suspensions, CTAB+SHNC, SDS+PTHC and CTAT have also been discussed in detail. Then we have given an overview of effects of electric field on the colloidal suspensions. Two types of geometries have been discussed: one in which the field is parallel to the plates and another when the field is perpendicular to the electrodes. Application of colloidal particles in diagnostic tests (Latex Agglutination Tests) has been discussed after this. Some methods used to enhance the sensitivity of LATs have also been reviewed. This is followed by a theoretical background of linear and non-linear rheology. We have also given an introduction to digital video microscopy, its advantages and discussed few quantities like pair correlation function, structure factor which can be extracted using digital video microscopy and particle tracking. The concluding part of this chapter describes the organization of this thesis. Chapter 2 discusses the experimental apparatus and techniques used in our studies. We describe our setup for applying the electric field to the colloidal particles and imaging and tracking their motion. We also discuss the image processing and analyzing methods for extracting the useful quantities from the digitized images. We have described the various components of the MCR-300 stress-controlled rheometer (Paar Physica, Germany) and the AR-1000N stress-controlled rheometer (T. A. Instruments, U. K.) followed by different experimental geometries that we have used for our experiments. Next we have described the various experiments that can be done using a commercial rheometer. Calculation of surface charge of colloidal particles using a conductivity meter has been demonstrated for our colloidal particle suspensions. We also describe the sample preparation methods employed in different experiments. In Chapter 3, we have discussed our study of clustering of colloidal particles under the influence of an ac electric field as a function of frequency. The field was applied in a direction perpendicular to the confining walls. Two regimes are observed, a low frequency regime where the clusters are isotropic with a local triangular order and a new high-frequency regime where the clusters are highly elongated (anisotropic) with no local order. The crossover from one regime to the other occurs at a critical frequency, fc. The formation of elongated clusters seen at high frequencies is explained in terms of rotation of particles due to a phase lag between the polarization of the electric double layer around a particle and the applied electric field that arises because of inhomogeneities of the conducting surface. We have also observed that the threshold field for the cluster formation, Eth, increases with frequency in both the regimes. We did these studies on two different sizes of particles and found that both Eth and fc were lower for the larger particles. Our model based on particle rotation was able to estimate the value of fc correctly for both the sizes of the particles. Chapter 4 describes a method employing an ac electric field applied perpendicular to the confining walls to increase the sensitivity of recognition of ligands by their corresponding receptors grafted on Brownian latex particles. Application of electric field assists the colloidal micro-particles grafted with receptors to come nearer due to electro-hydrodynamic drag. This increase in the local concentration of the latex particles results in improving the chances of ligand-receptor interaction leading to the aggregation of the latex particles. With this technique we have been able to increase the sensitivity of the ligand-receptor recognition by a factor as large as 50. We have demonstrated the utility of our method using streptavidin as the model receptor and biotinylated RNase A as the model ligand. We have also applied our technique to a commercially available kit for rheumatoid factor (RF) with successful results. The same method was also successfully applied for the detection of typhoid whose antibodies were purified and attached to polystyrene particles by our collaborators from DRDE Gwalior. In Chapter 5, we have studied the statics and dynamics of colloidal particles at different applied electric fields from zero to beyond the threshold field. We have taken a series of time-lapsed images and calculated out the pair-correlation function, mean squared displacement, structure factor, non-Gaussian parameter etc. We have studied both mono-dispersed colloidal system and binary colloidal system (mixture of two different sizes of particles). The aggregates formed in the two cases were analysed with the help of Voronoi polygons to quantify the microscopic structure. In mono-dispersed system, the aggregates formed were two-dimensional hexagonal crystals and we have used this system to study the freezing transition in 2-dimension. The properties of the system in the liquid and the crystalline state satisfy various criteria for the 2-d freezing transition. The first maximum of the structure factor at the voltage at which freezing occurs, is 5.5 as has been suggested for the 2-d freezing. This is reflected in the dynamics of the system also, where the ratio D/D0 falls below 10%, in accordance with the LPS (L¨owen, Palberg, Simon) criterion for freezing in 2-d colloidal systems [Phys. Rev. Lett. 70, 1557 (1993)]. However, in the binary colloidal system the clusters formed were not crystalline but more like 2-d dense liquids. A closer inspection of these clusters reveals that the motion of a smaller subset of particles is cooperative and follows string-like paths. The mean square displacement of such a system shows a plateau in the intermediate times which indicates the “caging” of particles by its neighbours. A peak in non-gaussian parameter indicates the presence of dynamical heterogeneities in the system. In Chapter 6, we have described the use of multiple particle tracking to study the microrheology of semidilute solutions of wormlike micelles and compared the results with those from macrorheology experiments done on the same samples. Two concentrations of CTAT (1.3% and 2%) were used. We observed that, in spite of the mesh size being much smaller than the size of the probe particles, the viscoelastic response function calculated using the one-point microrheology does not match with that measured from macrorheology. This can be attributed to the fact that there is another important length scale in the system, the mean micellar length, and it is comparable to the probe particle size. Two-point microrheology was successful in verifying the macrorheology results for CTAT 1.3% but it fails to do so for CTAT 2%. We attribute this to the fact that in a higher viscosity sample (2%), the hydrodynamic force propagate to a lesser distance, thereby limiting the measurable correlation between the particles and precluding the success of two-point microrheology. Chapter 7 describes a rheological study of aqueous solutions of varying concentration of cationic cetyltrimethyl ammonium bromide (CTAB) and anionic sodium-3-hydroxynapthalene-2-carboxylate (SHNC) kept at a fixed molar concentration ratio [CTAB]/[SHNC] = 2. At this molar ratio, the surfactants self-assemble into wormlike micelles which get entangled above the overlap concentration to form viscoelastic gel. The range of the total surfactant concentration φ varies from 1.17% to 5.16% by weight. We found that, plateau modulus, G0, shows a power law dependence on the surfactant concentration, φ, with an exponent 3, which is higher than the expected value of 2.25 observed for the one-component wormlike micelles. Zero shear viscosity, η0, and relaxation time, τR show a maximum at the surfactant concentration, φmax = 1.9% in contrast to a monotonic increase with φ. We propose that this non-monotonic behaviour is due to the unusual dependence of the average micellar length L ¯on φ, showing a maximum in average micellar length L at φmax. This argument provides a strong support to the model of micellar growth in the presence of electrostatic interactions developed by Mackintosh et. al [Europhys. Lett. 12, 697 (1990)]. The presence of electrostatic interactions also appears in the behaviour of the plateau modulus G0 that exhibits a larger φ dependence than in highly screened micelles. In the non-linear flow experiments, a minimum observed in critical shear rate (the shear rate at which shear thinning starts), ˙γc, at φmax strengthens our arguments. In Chapter 8, we describe the phase behaviour and rheology of SDS+PTHC (sodium dodecyl sulphate + p-toluidine hydrochloride) micellar solutions at different molar ratios α=[PTHC]/[SDS]) of the two components. At low values of α, polarizing microscopy observations reveal a transition from an isotropic to a nematic phase of disk-like micelles, whereas a transition to a lamellar phase occurs at higher α values > 0.5, on increasing the surfactant content. Linear rheology of the isotropic micellar solution reveal a viscous behaviour over a large range of surfactant concentrations. Surprisingly, this also extends to the nematic phase of disk-like micelles observed at α =0.2 and φ =0.35. These systems also exhibit a viscoelastic behaviour over a narrow range of surfactant concentration as reported in earlier studies. The extent of the viscoelastic region of the isotropic micellar solution also decreases with increase in α. Frequency sweep curves in this region, scaled on to a master curve is reminiscent of dilute suspensions of hard spheres or rigid Brownian rods. Consistent with the results from oscillatory shear measurements, the f;ow behaviour examined under steady shear is Newtonian over a large range of surfactant content in the isotropic micellar solution. An interesting result in these studies is the non-monotonic behaviour of the viscosity with increase in surfactant concentration. It is likely that the sharp rise in viscosity arises from a jamming effect of the rigid rods. Dynamic light scattering studies suggest that the drop in viscosity is due to the decrease in the length of the micellar aggregates. This is followed by a change in the morphology of the micelles from rods to disks as indicated by the transition to a nematic phase of disk-like micelles or a lamellar phase. A change in the morphology of micellar aggregates with increase in α is expected in mixed surfactant systems with strongly binding counterions. However, the surprising result is the change in morphology of the micellar aggregates with surfactant content. Such a behaviour is seen in mixed surfactant systems for the first time. The thesis concludes with a summary of our main results and a brief discussion of the scope of future work in Chapter 9.
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