Flow birefringence and rheological measurements on shear induced micellar structures

Aqueous solutions of cationic surfactant systems with strongly binding counterions show the striking phenomenon of shear induced phase transitions. At low shear rates or angular frequencies, the solutions exhibit Newtonian flow. At high rates of shear, however, the rheological properties change dramatically. Above a well defined threshold value of the velocity gradient, a supermolecular structure can be formed from micellar aggregates. This shear induced structure (SIS) behaves like a gel and exhibits strong flow birefringence. The formation of the shear induced structure is very complicated and depends on the specific conditions of the surfactant system. In this paper we discuss new results which have been obtained from rheological measurements and from flow birefringence data. We examine the stability of the shear induced state as a function of temperature, surfactant concentration and salt concentration and we analyse the effect of solubilisation of alcohols and hydrocarbons. The results are interpreted in terms of a kinetic model which accounts for the observed behavior.Dedicated to the 60. birthday of Prof. H. Harnisch, Hoechst AGPartly presented at the 2nd Conference of European Rheologists, Prague, June 17–20, 1986     

Extensional flow resistance of dilute polyacrylamide and surfactant solutions

The extensional flow behaviour of dilute aqueous solutions of a partiallyhy-drolyzed polyacrylamide and a surfactant were investigated in an extensional flow cell. The cell was designed such that fluids were subjected to steady shear before undergoing extensional motion in a converging channel. Extensional resistance was monitored by measuring the pressure drop through the channel. Such measurements were made over a range of extensional rates at fixed values of the upstream shear rate. Solutions of different concentrations were tested — up to 40 ppm of polyacrylamide and 450 ppm of surfactant — at various temperatures in the case of surfactant and for different types and amounts of salt in the case of polyacrylamide. Of the results, the more notable are that the extensional resistance of polyacrylamide solutions is affected much more by CaCl₂ than by NaCl and that surfactant solutions do not exhibit extensional resistance unless they are pre-sheared.     

Response of blood flow through an artery under stenotic conditions

This paper presents an analytical study on the behavoiur of blood flow in an artery having a stenosis. This is basically formulated through the use of a suitable mathematical model. The arterial segment under consideration is simulated by an anisotropically elastic cylindrical tube filled with a viscous incompressible fluid representing blood. The analysis is carried out for an artery with mild local narrowing in its lumen forming a stenosis. Particular emphasis has been paid to the effect of the surrounding connective tissues on the motion of the arterial wall. Blood is treated as a Newtonian fluid. The analysis is restricted to propagation of small amplitude harmonic waves, generated due to the flow of blood whose wave length is large compared to the radius of the arterial segment. The effect of the shape of stenosis on the resistance to blood flow has been well illustrated quantitatively through numerical computations of the resulting expressions. A quantitative analysis is also made for the variation of the phase velocity, as well as the velocity of wave propagation and the flow rate, in order to illustrate the applicability of the model.     

Statistical mechanics of temporary polymer networks

The statistical theory of temporary polymer networks developed in parts I and II of this work is closed by a discussion on dynamical effects, including comparison with experiments. After a short review of the theory developed in parts I and II we discuss the situation in which a prescribed velocity gradient is imposed on the physical system formed by the temporary network and the solvent. The dynamical equation for the 2nd moments (derived from a generalized bead-spring model) contains the configuration-dependent transition probability, which depends on the second moments in a complex way. An approximate solution of these equations is obtained from a computer program. It shows the experimentally observed behavior, in particular the stress overshoot maximum after a sudden start of the flow.The derivation of the above equations contains simplifying assumptions which, however, leave the essential physics intact. The most important assumptions concern the relaxation time approach and the decay and formation processes. These were supposed to be dilute enough to break up the many-junction processes into one-junction processes. Both assumptions are analogous to frequently used assumptions in Boltzmann's kinetic theory.     

Numerical solution for the flow of viscoelastic fluids around an inclined circular cylinder.

Finite difference solutions have been obtained by the perturbation method to investigate the influence of shear thinning and elasticity on the flow around an inclined circular cylinder of finite length in a uniform flow. In this numerical analysis a generalized upper-convected Maxwell model, in which the viscosity changes according to the Cross model, has been used.The local flow over the cylinder is only slightly deflected. However, in the wake flow behind the cylinder the particle path is remarkably influenced by the axial flow and rapidly flows up parallel to the cylinder's axis. Then it gradually rejoins direction of the incoming flow. It is found that viscoelastic fluids are prone to flow axially in the vicinity of the cylinder. The numerical predictions generally agree with the flow visualization results.The numerical solutions also demonstrate that elasticity has a strong effect on the velocity profile especially around both ends of the cylinder; elasticity increases the asymmetric profiles of both circumferential velocity and axial velocity with respect to equal to 90° and decreases a difference in the circumferential velocity between the windward end and the leeward end.For non-Newtonian fluids, the length of the wake flow is influenced by not only the Reynolds number but also the cylinder diameter and it is larger for the cylinder with the smaller diameter at the same Reynolds number.Partly presented at the 9th Australasian Fluid Mechanics Conference, University of Auckland, New Zealand, 8–12 December, 1986     

Pressure driven flow of dilute polymer solutions in a channel: Analytic results for very small and for very large channels

Kinetic theory of dilute macromolecular solutions is applied to pressure driven flow in a small channel where wall- (and interfacial) layers have to be reckoned with. The complete rheology is studied. It turns out that for very small channels both the shear stress and the normal stress are an order of magnitude larger than corresponding quantities in simple shear. On the other hand, when the channel is so wide that the wall layers are very thin in comparison, agreement with results appropriate for simple shear is found. The volume flow rate-pressure difference relation is derived and compared to the prediction which utilizes the slip velocity concept. For very small channels, this concept is five orders of magnitude off, but reproduces asymptotically correct results for very large channels.     

Shear and extensional flow of polyacrylamide solutions

As part of an EEC Science Stimulation programme on extensional viscosity two major conferences were organised on the subject. The second of these was devoted to the results obtained on a standard fluid, M 1. The data obtained in shear flow was remarkably consistent from laboratory to laboratory. Extensional flow results presented quite a different picture. Using a series of nonequilibrium techniques such as the spinline rheometer, opposing jet, falling drop and converging flow, extensional viscosity results were obtained which differed by as much as two to three orders of magnitude. Nevertheless, it was apparent that consistancy did exist between similar techniques. It is in the context of this information that the measurements described below have been made.The shear and extensional flow properties of partially ionised polyacrylamide in solution at concentrations ranging from 5 ppm were measured. The method of solution preparation was found to have a profound effect on the behaviour of the solutions in shear flow. The influence of salt concentration and pH was investigated and is discussed in the context of molecular shape in solution.Extensional flow measurements, using the spinline rheometer, show that the solutions are strongly strain thickening even at concentrations as low as 5 ppm. These results are considered in the light of polymer entanglement and association in the strong flow field.Delivered as a Keynote Lecture at the Golden Jubilee Conference of the British Society of Rheology and Third European Rheology Conference, Edinburgh, 3–7 September, 1990.     

Analysis of Taylor vortex flow by means of laser light scattering

Rheological measurements and light-scattering experiments were performed on dilute solutions of high molecular polystyrene. We are able to describe the orientation behavior of chain molecules under shear flow by means of light-scattering. Beyond that these investigations of light-scattering of flowing polymer solutions are an useful and suitable tool for detection and characterization of Taylor vortex formation. We can estimate the appearance of these hydrodynamic instabilities, which overlay the laminar main flow and we can observe a typical influence of the solvent power on it.Presented in part at the meeting of the Deutsche Rheologische Gesellschaft, Berlin, 13–15 May, 1991.     

Untersuchungen zum Fließverhalten verschieden konzentrierter Polyisobutenlösungen unter hoher Scherbeanspruchung.

Zusammenfassung Das Schubspannungs- und Verfestigungsverhalten verschieden konzentrierter hochmolekularer Polyisobutenlösungen wird mit Hilfe eines neu konstruierten Hochdruckkapillarviskosimeters bis zu sehr hohen Schergeschwindigkeiten untersucht. Hierbei wird gleichzeitig der Einlaufdruckverlust nach Bagley durch Messungen an Kapillaren mit unterschiedlichenL/R-Verhältnissen ermittelt und, um Informationen über das Einströmverhalten der Lösungen zu erhalten, die Einlaufströmung in die Kapillare sichtbar gemacht. Im Bereich niedriger Schergeschwindigkeiten werden die Lösungen zusätzlich mit verschiedenen Rotationsviskosimetern charakterisiert.Die anhand der durchgeführten Untersuchungen erhaltenen Fließkurven lassen sich für Lösungen mit einem Polymergehalt ab 0,5% PIB-B200 in drei Bereiche einteilen, die mit Hilfe von Strömungssichtbarmachungsuntersuchungen verschiedenen Strömungsphänomenen zugeordnet werden können. Dabei kommt es u. a. zu Verfestigungserscheinungen, die sich in einem sprunghaften Ansteigen des Druckverlustes bemerkbar machen. Durch Messungen an Kapillaren mit einem kegelförmigen Einlauf kann gezeigt werden, daß diese Verfestigungserscheinungen und der damit verbundene Druckanstieg nicht nur auf das Auftreten von Sekundärströmungen im Einlaufbereich der Kapillaren zurückgeführt werden kann, sondern daß hierfür andere Effekte wie etwa die Bildung von Assoziaten aus Makromolekülen verantwortlich gemacht werden können. Auch die starke Viskositätszunahme der Lösungen im Verfestigungsbereich und die Beobachtung der Ausbildung heller Streulichtfelder sprechen für eine Bildung von Polymerassoziaten vor der Kapillare.Des weiteren wird bei den Untersuchungen zur Bagley-Korrektur festgestellt, daß zur korrekten Ermittlung des Einlaufdruckverlustes bei höher konzentrierten Polyisobutenlösungen Kapillaren mit einemL/R-Verhältnis von mindestens 1000 verwendet werden müssen. Es zeigt sich nämlich im Bagley-plot dieser Lösungen, daß die Linien konstanter Schergeschwindigkeit bei kleinerenL/R-Verhältnissen eine auffallende Krümmung im Sinne eines mit zunehmendemL/R-Verhältnis abnehmenden Druckgradienten besitzen, der erst oberhalb eines bestimmtenL/R-Verhältnisses konstant wird.

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A new design high-pressure capillary-viscometer is used to study the shear behavior of high-molecular polyisobutene solutions up to very high shear rates. The entry pressure loss from the Bagley-plot is estimated by the measurement in capillaries of different length-to-radius (L/R) ratios. Simultaneously, flow visualization of the entry flow is carried out. At low shear rates the flow behavior of the solutions is characterized by different rotational viscometers.The obtained flow curves for the solutions with polymer concentrations being above 0.5% PIB-B200 can be divided into three regions which can be related to different flow phenomena by means of flow visualization. A sudden increase in pressure loss can be related to a shear thickening behavior. Measurements in capillaries with a conical entry show that this thickening behavior is not only due to secondary flows in the entry region of the capillary, but also due to other effects like the association of macromolecules. The assumption of the formation of molecular associates is also supported by the large increase in the viscosity of the solutions in the thickening region and the observed formation of luminous scattered light areas.Furthermore, the investigations on the Bagley-correction show that for higher concentrated polyisobutene solutions capillaries withL/R ratios of at least 1 000 have to be used for a correct determination of the entry pressure loss. The Bagley-plots of these solutions show that lines of constant shear rate are remarkably curved at lowerL/R ratios. The gradient of the pressure loss decreases with increasingL/R ratio and approaches a constant value at a certainL/R ratio.

Erster Teil einer vom Fachbereich Chemietechnik der Universität Dortmund genehmigten Dissertation.     

Newtonian stratified flow through an abrupt expansion

The present paper is devoted to the numerical simulations of stratified generalized Newtonian flow. The main feature of the algorithm is to include the coordinates of the interface as primitive unknowns of the flow problem together with the nodal velocity components and pressures calculated on a deformable finite element mesh. Newton-Raphson's iterative method is used for solving the non-linear problem. Special attention is given to the location of the intersection between the interface and a solid boundary, when it is unknown at the outset. The method is applied to the creeping stratified flow of two Newtonian fluids through a one-to-four abrupt expansion; the results remain valid for the contraction problem. It is found that, under appropriate conditions, the small Newtonian corner vortex can increase by a large factor, both in size and intensity; the degrees of freedom of the simulation are the ratios of flow-rate and of viscosity of the fluids.     

The flow past a sphere in a cylindrical tube: effects of intertia,shear-thinning and elasticity

Numerical solutions are presented for the flow past a sphere placed at the centreline of a cylindrical tube for Reynolds numbers ranging from 0 to 150, using a boundary element method. Fluids are modelled by a variety of constitutive equations including the Newtonian, the Carreau and the Phan-Thien-Tanner models. The influence of inertia, shear-thinning and fluid elasticity on the flow field, drag and the pressure drop force-drag ratio is examined. Some results are compared with available experimental data.     

Formation des gels d'agar et seuil d'écoulement

Résumé Les seuils de plasticité de gels d'agar a différentes concentrations ont été déterminés par différentes méthodes et comparé entre eux. Le seuil de contrainte qui apparaît au cours du refroidissement de la solution indique le début de la formation du réseau gélifié. II définit une température d'apparition du seuil de plasticite. La determination de cette temp6rature critique montre que la formation du gel est soumis aux conditions de refroidissement de la solution: le processus de gelification est accéléré par un refroidissement rapide des solutions et débute à une température plus basse. La formation du gel peut être suivie dans des conditions plus proches des réalités industrielles de fabrication de ces milieux.

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The yield stress of agar gels has been measured by different methods and the results compared. The yield stress which occurs during cooling of polymer solutions indicates the beginning of crystalline network formation. This point defines the temperature of plastic flow; its determination shows that the gel formation is subordinated to cooling conditions of the solution: the process of gelification is retarded by very fast cooling, and is induced at a lower temperature than occurs with slow cooling. We follow the formation of gels in conditions similar to those used in manufacturing processes.

     

Different behaviors of concentrated polysaccharide systems in large-amplitude oscillating shear fields

Two series of oscillatory flow tests were carried out on two concentrated polysaccharide systems (hydroxyethyl guar gum and scleroglucan) in order to evaluate the possibilities offered by large-deformation techniques for the discrimination between different classes of macromolecular systems (i.e., entanglement networks and weak gels). Frequently and strain sweeps, as well as combined steady and oscillatory shear tests were performed to analyze the influence of strain amplitude and of the superposed parallel shear rate on the dynamic properties of these materials.     

Influence of the formation of associations of macromolecules on the rheo-optical properties of their dilute solutions. II. Comparison with experimental results

The results of the theory presented in part I are compared to already published flow birefringence data obtained with dilute up to semi-dilute solutions of polyethylene oxide which have also shown shear thickening effects. The agreement with the theory is quite good so that the reversible formation of associations in flow seems to be a process which has to be taken in account for high molecular weight flexible macromolecules solutions in relatively poor solvents.     

Wall effects in the flow of flexible polymer solutions through small pores

Effective viscosities of dilute and semidilute flexible solutions flowing through small cylindrical pores were determined in the Newtonian regime for various pore diameters. The low viscosities relative to the bulk were associated with a depletion phenomenon due to a steric exclusion of macromolecules from the pore wall. Using a two-fluid flow model, the depletion layer thickness was determined and discussed as a function of polymer concentration, ionic strength, and molecular weight. This thickness, which was constant and close to the macromolecule gyration radius in dilute regime, was found to decrease rapidly with polymer concentration in the semidilute regime.     

Elastic recovery and polymer-polymer interactions

i) Elastic recovery in polymeric liquids is a cooperative phenomenon in the sense that individual polymer molecules undergoing retraction must interact with one another in order to generate recovery. Stress generated by polymer molecules under an externally imposed flow field may or may not be a cooperative phenomenon. We suggest that the ability to describe the large elastic recovery exhibited by many polymeric liquids furnishes a crucial test of the validity of methods used to model the interaction of a given polymer molecule with its neighbors. Temporary-junction network models appear to be capable of explaining observed recoveries. Elastic recovery cannot be explained by single-molecule-in-a-mean-field theories which involve no calculation of the effect of the single molecule on the mean field. ii) A Gaussian network theory equation for the change of volume with elongation for a cross-linked elastomer is generalized in order to allow the bulk compliance to depend on elongation. iii) It is proved that two classes of flow history, namely shear-free and shear, are constitutively independent in the sense that, for a given viscoelastic liquid of unknown constitutive equation, the behavior in one class cannot be predicted from rheological measurements (however extensive) made solely in the other class.Dedicated to Prof. Dr. J. Meissner on the occasion of his 60th birthday.     

Numerical simulation of delayed die swell

In a recent paper, Joseph et al. showed that, for a number of viscoelastic fluids, one can observe the phenomenon of delayed die swell beyond a critical extrusion velocity, or beyond a critical value of the viscoelastic Mach number. Giesekus had also observed that delayed die swell is a critical phenomenon.In the present paper, we find a set of material and flow parameters under which it is possible to simulate delayed die swell. For the viscoelastic flow calculation, we use the finite element algorithm with sub-elements for the stresses and streamline upwinding in the discretized constitutive equations. For the free surface, we use an implicit technique which allows us to implement Newton's method for solving the non-linear system of equations. The fluid is Oldroyd-B which, in the present problem, is a singular perturbation of the Maxwell fluid. The results show very little sensitivity to the size of the retardation time. We also show delayed die swell for a Giesekus fluid.This paper is dedicated to Professor Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

Shear-induced structures in macroscopic dispersions

Observations are reported on structures induced in an oscillatorily sheared dispersion of glass spheres in a silicon oil and in a highly viscoelastic fluid (mixture of polyisobutylenes). The shear flow used in these experiments is oscillatory with a frequency 200 Hz) and has displacement amplitudes of the order of magnitude as the sphere diameter (40 µm).The interpretation of the structures observed is based on non-linear effects which, even when small, in comparison to the viscous effects, may lead to the irreversible formation of structures over a long time, i.e. a time much larger than the period of the shear. A comparison between similar experiments performed with two different suspending fluids (silicon oil, in which the spheres line up perpendicular to the velocity direction; polyisobutylene mixture, in which the spheres line up in the velocity direction) confirm our interpretation.