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.     

Stability of Couette flow of liquids with power law viscosity

The stability of the Couette flow of the liquid with the power law viscosity in a wide annular gap has been investigated theoretically in this work with the aid of the method of small disturbances. The Taylor number, being a criterion of the stability, has been defined using the mean apparent viscosity value in the main flow. In the whole range of the radius ratio, R _i /R _o and the flow index, n, considered (R _i /R _o 0.5, n = 0.25–1.75 ), the critical value of the Taylor number Ta _c is an increasing function of the flow index, i.e., shear thinning has destabilizing influence on the rotational flow, and dilatancy exhibits an opposite tendency.In the wide ranges of the flow index, n > 0.5, and the radius ratio, R _i /R _o > 0.5, the wide-gap effect on the stability limit is predicted to be almost the same for non-Newtonian fluids as for Newtonian ones. The ratio on the critical Taylor numbers for non-Newtonian and Newtonian fluids: Ta _c (n) and Ta _c (n = 1) obey a generalized functional dependence: Ta _c (n)/Ta _c (n = 1) = g(n), where g(n) is a function corresponding to the solution for the narrow gap approximation.Theoretical predictions have been compared with experimental results for pseudoplastic liquids. In the range of the radius ratio R _i /R _o > 0.6 the theoretical stability limit is in good agreement with the experiments, however, for R _i /R _o < 0.6, the critical Taylor number is considerably lower than predicted by theory.     

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.     

Prediction of the non-linear rheological properties of polymer solutions by means of the Rouse-Zimm model with slippage

The non-affine deformation of macromolecules and the slippage function are discussed. In case of polymer solutions with moderate concentration the slippage function is determined by means of the Cox-Merz rule. The non-linear viscoelasticity of these solutions is described with the aid of the Rouse-Zimm model with slippage function. The theoretical predictions show good agreement with published experimental data.     

Attempts to find a molecular theory for which the high-frequency dynamic viscosity is less than the solvent viscosity

It has been found that for some dilute polymer solutions the dynamic viscosity at very high frequencies is less than the zero-shear-rate solvent viscosity. Such an effect cannot be explained by the usual kinetic theories using bead-spring-rod models. Here we examine several modifications of the kinetic theories that might be expected to explain the experimental facts.This paper is dedicated to Prof. Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

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.     

The steady shear viscosity of filled polymeric liquids described by a linear superposition of two relaxation mechanisms

Filled polymeric liquids often exhibit apparent yielding and shear thinning in steady shear flow. Yielding results from non-hydrodynamic particle—particle interactions, while shear thinning results from the non-Newtonian behavior of the polymer melt. A simple equation, based on the linear superposition of two relaxation mechanisms, is proposed to describe the viscosity of filled polymer melts over a wide range of shear rates and filler volume fraction.The viscosity is written as the sum of two generalized Newtonian liquid models. The resulting equation can describe a wide range of shear-thinning viscosity curves, and a hierarchy of equations is obtained by simplifying the general case. Some of the parameters in the equation can be related to the properties of the unfilled liquid and the solid volume fraction. One adjustable parameter, a yield stress, is necessary to describe the viscosity at low rates where non-hydrodynamic particle—particle interaction dominate. At high shear rates, where particle—particle interactions are dominated by interparticle hydrodynamics, no adjustable parameters are necessary. A single equation describes both the high and low shear rate regimes. Predictions of the equation closely fit published viscosity data of filled polymer melts. n power-law index - n ₁,n ₂ power-law index of first (second) term - shear rate - steady shear viscosity - ₀ zero-shear rate viscosity - _{0, 1}, _{0, 2} zero-shear rate viscosity of first (second) term - time constant - ₁, ₂ time constant of first (second) term - µ _r relative viscosity of filled Newtonian liquid - ₀ yield stress - ø solid volume fraction - ø _m maximum solid volume fraction     

Measurements of slip at the wall during flow of high-density polyethylene through a rectangular conduit

A hot-film probe has been used to measure slip of high-density polyethylene flowing through a conduit with a rectangular cross section. A transition from no slip to a stick-slip condition has been observed and associated with irregular extrudate shape. Appreciable extrudate roughness was initiated at the same flow rate as that at which the relationship between Nusselt number and Péclet number for heat transfer from the probe departed from the behavior expected for a no-slip condition at the conduit wall. A ₁ constant defined by eq. (A3) - C dimensionless group used in eq. (7) - C _p heat capacity - D constant in eq. (13) - f u _s/u - f _lin defined by eq. (A6) - G storage modulus - G loss modulus - k thermal conductivity - L length of hot film in thex-direction - L _eff effective length of large probe found from eq. (A3) - Nu _L Nusselt number, defined for a lengthL by eq. (2) - (Nu _L)₀ value ofNu _L atPe = 0 (eq. (A 1)) - Pe Péclet number,uL/ - Pe ₀ Péclet number in slip flow, eq. (6) - Pe ₁ Péclet number in shear flow, eq. (4) - q _L average heat flux over hot film of lengthL - R _i resistances defined by figure 8 - R _AB correlation coefficient defined by eq. (14) for signalsA andB - T temperature - T _s temperature of probe surface - T ambient temperature - T T _s –T - u average velocity - u _s slip velocity - V _b voltage indicated in figure 8 - W probe dimension (figure 6) - x distance in flow direction (figure 1) - y distance perpendicular to flow direction (figure 1) - thermal diffusivity,k/C _p - wall shear rate - _5% thickness of lubricating layer during probe calibration for introduction of an error no greater than 5%; see Appendix I - ^* complex viscosity - density - time - _c critical shear stress, eq. (13) - _w wall shear stress - frequency characterizing extrudate distortion (figures 12 and 13), or frequency of oscillation during rheometric characterization (figures 18–20) - * quantity obtained from normalized Nusselt number, eq. (A1), or complex viscosity ^* - A actual (small) probe (see Appendix I) - M model (large) probe (see Appendix I)     

Transient stress responses predicted by the internal viscosity model in elongational flow

Predictions are made for the elongational-flow transient rheological properties of the dilute-solution internal viscosity (IV) model developed earlier by Bazua and Williams. Specifically, the elongational viscosity growth function _e ⁺ (t) is presented for abrupt changes in the elongational strain rate . For calculating _e ⁺, a novel treatment of the initial rotation of chain submolecules is required; such rotation occurs in response to the macroscopic step change of at t = 0. Representative are results presented for N = 100 (N = number of submolecules) and = 1000 f and 10000 f (where is the IV coefficient and f is the bead friction coefficient), using h ^* = 0 (as in the original Rouse model) for the hydrodynamic interaction. The major role of IV is to cause the following changes relative to the Rouse model: 1) abrupt stress jump at t = 0 for _e ⁺; 2) general time-retardance of response. There is no qualitative change from the Rouse-model prediction of unbounded il growth when exceeds a critical value ( ), and calculations of submolecule strains at various show that the unbounded- _e ^– behavior arises from unlimited submolecule strains when . However, the time-retardance could delay such growth beyond the timescale of most experiments and spinning processes, so that the instability might not be detected. Finally, _e ⁺ (t) and _e ( ) in the limit are presented for N = 1 and compared with exact predictions for the analogous rigid-rod molecule; close agreement lends support for the new physical approximation introduced for solving the transient dynamics for any N.     

The rheology of a smectic main-chain polymer

The rheology of a smectic main-chain polymer shows that the activation energy is high (275 kJ mol^–1) and that the viscosity is more than two orders of magnitude higher than in the isotropic phase. The recoverable strain in the smectic phase is largely due to the reformation of the smectic layers after cessation of shear.     

Effect of processing and particulate fillers on the rheology of a nematic polymer melt

Processing of a nematic HBA/HNA polymer melt increases the capillary diameter dependence of the viscosity and induces structural changes which are evident in oscillatory shear, but cannot be characterized by DSC. The effect of 6-m calcium carbonate particulate fillers is to increase the viscosity uniformly. Low concentrations of sub-micron carbon black particles cause an unexplained viscosity minimum in a large (30-mil) capillary.     

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     

Experimental investigations of the stability limit of the helical flow of pseudoplastic liquids

The stability of the laminar helical flow of pseudoplastic liquids has been investigated with an indirect method consisting in the measurement of the rate of mass transfer at the surface of the inner rotating cylinder. The experiments have been carried out for different values of the geometric parameter = R ₁/R ₂ (the radius ratio) in the range of small values of the Reynolds number,Re < 200. Water solutions of CMC and MC have been used as pseudoplastic liquids obeying the power law model. The results have been correlated with the Taylor and Reynolds numbers defined with the aid of the mean viscosity value. The stability limit of the Couette flow is described by a functional dependence of the modified critical Taylor number (including geometric factor) on the flow indexn. This dependence, general for pseudoplastic liquids obeying the power law model, is close to the previous theoretical predictions and displays destabilizing influence of pseudoplasticity on the rotational motion. Beyond the initial range of the Reynolds numbers values (Re>20), the stability of the helical flow is not affected considerably by the pseudoplastic properties of liquids. In the range of the monotonic stabilization of the helical flow the stability limit is described by a general dependence of the modified Taylor number on the Reynolds number. The dependence is general for pseudoplastic as well as Newtonian liquids.Nomenclature C _i concentration of reaction ions, kmol/m³ - d = R ₂ –R ₁ gap width, m - F _M () Meksyn's geometric factor (Eq. (1)) - F ₀ Faraday constant, C/kmol - i _l density of limit current, A/m³ - k _c mass transfer coefficient, m/s - n flow index - R ₁,R ₂ inner, outer radius of the gap, m - Re = V _m ·2d·/µ _m Reynolds number - Ta _c = _c ·d^3/2·R ₁ ^1/2 ·/µ _m Taylor number - Z _i number of electrons involved in electrochemical reaction - = R ₁/R ₂ radius ratio - µ apparent viscosity (local), Ns/m² - µ _m mean apparent viscosity value (Eq. (3)), Ns/m² - µ _i apparent viscosity value at a surface of the inner cylinder, Ns/m² - density, kg/m³ - _c angular velocity of the inner cylinder (critical value), 1/s     

Representation of the rheological properties of polymer melts in terms of complex fluidity

In dynamic rheological experiments melt behavior is usually expressed in terms of complex viscosity ^* () or complex modulusG ^* (). In contrast, we attempted to use the complex fluidity ^* () = 1/µ ^* () to represent this behavior. The main interest is to simplify the complex-plane diagram and to simplify the determination of fundamental parameters such as the Newtonian viscosity or the parameter of relaxation-time distribution when a Cole-Cole type distribution can be applied. ^* () complex shear viscosity - () real part of the complex viscosity - () imaginary part of the complex viscosity - G ^* () complex shear modulus - G() storage modulus in shear - G() loss modulus in shear - J ^* () complex shear compliance - J() storage compliance in shear - J() loss compliance in shear - shear strain - rate of strain - angular frequency (rad/s) - shear stress - loss angle - ^* () complex shear fluidity - () real part of the complex fluidity - () imaginary part of the complex fluidity - ₀ zero-viscosity - ₀ average relaxation time - h parameter of relaxation-time distribution     

Mesophase formation in high molecular-weight xanthan solutions

After a short review of theoretical background on mesophase formation in polymer solutions, this paper describes the liquid crystal phase transition and the corresponding rheological properties for aqueous solutions of a high-molecularweight xanthan sample (M _w 1.8 10⁶). The formation of mesophases has been studied using polarizing microscopy and viscometry. The effects of the presence of salts, bacteria cells and proteins have been investigated. The variations in the viscosity, due to mesophase formation, are in qualitative agreement with the predictions of Matheson's theory, but the onset of the ordered phase occurs at very low polymer concentrations and the diphasic domain is much broader than predicted by thermodynamic models. These characteristics of the phase transition are related to the very high molecular weight of the sample studied and can be explained mainly by the effects of cooperative interactions between xanthan chains and of chain flexibility reducing translational entropy.     

Stabilität der ebenen Couette-Strömung bezüglich Störungen in der viskosimetrischen Ebene

Zusammenfassung Die Stabilität der ebenen Scherströmung eines einfachen Fluids wird im Rahmen der Kurzwellenapproximation für Störungen in der viskosimetrischen Ebene untersucht. Für kurze Wellen ist eine Stabilitätsanalyse unabhängig von der speziellen Form der Stoffgleichung möglich. Die vorliegende Analyse stellt einen ersten Schritt in diese Richtung dar und führt zu einem hinreichenden Stabilitätskriterium. Für kurze Wellen sind die Maxwell-FlüssigkeitenA undB bezüglich ebener Störungen stabil.

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The stability of a plane shear flow of simple fluids is investigated for perturbations in the viscometric plane within the framework of the short wave approximation. For short waves it is possible to carry out a stability analysis, which is independent of the type of constitutive equation. The analysis presented is the first step in this direction and leads to a sufficient stability criterion. For short waves Maxwell fluidsA andB are stable for perturbations in the viscometric plane.

Korrespondenz bitte an diese Adresse richten     

Einfluß nichtnewtonscher Stoffeigenschaften auf die Taylor-Wirbelströmung

Zusammenfassung Nach einer kurzen Beschreibung über die Anwendung der Taylor-Wirbelströmung bei der Filtration von nichtnewtonschen Flüssigkeiten werden polymere Modellflüssigkeiten charakterisiert, die als Partikel- und Netzwerklösungen in einer Wirbelströmungsapparatur eingesetzt wurden. Die Fließkurven der Polymerlösungen zeigen aufgrund der extrem hochmolekularen Polymerproben neben strukturviskosen Erscheinungen auch dilatantes Fließverhalten mit besonderer Wirkung auf die Taylor-Wirbelströmung.Die Versuchsflüssigkeiten offenbaren vier verschiedene Typen von Strömungsinstabilitäten: spiralförmige, schwingende und stationäre Instabilitäten sowie gedämpfte Turbulenz. Während die stark strukturviskosen Netzwerklösungen alle genannten Formen aufweisen, fehlt bei den Partikellösungen die spiralförmige Instabilität.Unter Zuhilfenahme des Hantelmolekülmodells zur Beschreibung viskoelastischer Strömungsphänomene gelingt es, durch Einführung einer kritischen Deborahzahl den Einsatzpunkt nichtnewtonscher Taylorströmungseffekte vorauszusagen. Die gefundene Beziehung steht in engem Zusammenhang mit dehnviskositätserhöhenden Polymerwirkungen in Porenströmungen und mit reibungsmindernden Polymereffekten in turbulenten Rohrströmungen.

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Experimental investigations dealing with dilute polymer solutions are described after a short review of the application of Taylor-vortex flow in the filtration processes of non-Newtonian fluids. The test fluids represent both viscoelastic solutions with isolated macromolecules and network solutions with power law fluid behaviour.These solutions show four different types of flow instabilities: spiral-shaped, oscillatory, steady and turbulent phenomena. The Taylor-numbers which depend upon the polymer concentration are determined for the onset of these instability types. For isolated macromolecule solutions, the Deborah-number concept for dilute dumbbell solutions can be applied to describe the first appearance of irregular nonstationary Taylor vortices.The present data are compared to literature values. This fluid behaviour is related to extensional viscosity increases which are also observed in porous media flow and turbulent pipe flow of dilute macromolecular solutions.

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Nomenklatur A, B Konstanten aus Randbedingungen der Ringspaltströmung - C Polymerkonzentration - D Schergeschwindigkeit - De Deborahzahl - l Länge einer Wirbelzelle - L Zylinderlänge - m Gesamtanzahl der Wirbelpaare zur Bestimmung der Wellenzahl - M Molmasse der Polymere - M _w Gewichtsmittel der Molmasse - M _v Viskositätsmittel der Molmasse - n Drehzahl des Rotors - universelle Gaskonstante - r Radius - R _a Radius des Außenzylinders - R _i Radius des Innenzylinders - s Spaltweite - s ^* dimensionslose Spaltweite - T Temperatur - Ta Taylorzahl - v Umfangsgeschwindigkeit - z Anzahl der Wirbelpaare zur Bestimmung der Wellenzahl Griechische Symbole Deformationskoeffizient von Makromolekülen - Wellenzahl - Dehnrate - dynamische Viskosität - [] Grenzviskositätszahl - Relaxationszeit - Dichte - Schubspannung - Winkelgeschwindigkeit - _a Winkelgeschwindigkeit des Außenzylinders - _i Winkelgeschwindigkeit des Innenzylinders Indices c kritisch (erstmaliges Auftreten von Taylorwirbel) - N newtonsch - o onset, Schwellwert - P polymer - r radial - Sch schwingend - Spir spiralförmig - Stat stationär - Turb turbulent - T Taylorströmung - Umfangsrichtung Herrn Prof. Dr. Heinz Harnisch zum 60. Geburtstag gewidmet     

A purely elastic transition in Taylor-Couette flow

Experimental evidence of a non-inertial, cellular instability in the Taylor-Couette flow of a viscoelastic fluid is presented. A linear stability analysis for an Oldroyd-B fluid, which is successful in describing many features of the experimental fluid, predicts the critical Deborah number,De _c , at which the instability is observed. The dependence ofDe _c on the value of the dimensionless gap between the cylinders is also determined.This paper is dedicated to Professor Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

A differential constitutive equation for polymer melts

A modification of the Giesekus constitutive equation is derived by incorporating (approximately, via the Peterlin approximation) the finite extensibility of polymer molecules into dumbbell kinetic theory along with the anisotropic hydrodynamic drag suggested by Giesekus. The constitutive equation that is obtained retains much of the simplicity of Giesekus' constitutive equation, but it involves terms that are cubic in the stress as well as those that are quadratic. It is shown that the constitutive equation quantitatively describes the steady elongational viscosity of the IUPAC polymer melt A (including the strain softening of the melt), but it cannot describe the elongational and shear viscosities simultaneously. It is also shown that the constitutive equation satisfies the Lodge-Meissner relation for shear strains less than unity.