Microsecond relaxation processes in shear and extensional flows of weakly elastic polymer solutions

In this paper, we introduce an experimental protocol to reliably determine extensional relaxation times from capillary thinning experiments of weakly elastic dilute polymer solutions. Relaxation times for polystyrene in diethyl phthalate solutions as low as 80?μ s are reported: the lowest relaxation times in uniaxial extensional flows that have been assessed so far. These data are compared to the linear viscoelastic relaxation times that are obtained from fitting the Zimm spectrum to high frequency oscillatory squeeze flow data measured with a piezo-axial vibrator (PAV). This comparison demonstrates that the extensional relaxation time reduced by the Zimm time, λ _ext/λ _z, is not solely a function of the reduced concentration c/c*, as is commonly stated in the literature: an additional dependence on the molecular weight is observed.     

Measurement of extensional viscosity of polymer solutions

A filament stretching technique for measuring the extensional viscosity of polymer solutions at constant stretch rate is presented. The liquid sample is held between two coaxial discs and stretched by moving the bottom disc downwards with a speed that increases exponentially with time. This is illustrated using a constant viscosity, elastic fluid consisting of 0.185% polyisobutylene in a solvent of kerosene and polybutene. For the case of this particular fluid, two distinct stretch rate regions are found to arise. The stretch rate in the first region is much higher than in the second, which is, in most cases, close to the overall stretch rate imposed on the sample. Nonetheless, all the results of any given run can be represented using an average extensional rate. The extensional stress growth data, plotted as the Trouton ratio against time, show an initial linear viscoelastic region where T_R rises to a value of 3, independent of extensional rate. Beyond this region, T_R depends on the stretch rate and rises dramatically to values in excess of 10³; the higher the extensional rate, the faster is the increase in T_R. These data do not seem to reach a steady state and appear to be similar to polymer melt data obtained by others in the past. The reproducibility of the results is very good and all this suggests that it is now possible to obtain unambiguous constant-stretch-rate stress-growth data for polymer solutions stretched from a state of rest.     

Stress relaxation of a polymer melt after extensional flow

The relaxation behaviour of a stretched polymer melt is described with the aid of the semi-empirical constitutive equation of Wagner. The theoretical predictions based on this model, are in fair agreement with the experimental results, as far as the period of stress decay following the stress build-up is not too long.     

Theory of dilute polymer solutions in viscoelastic fluid with a single relaxation time

Rheological equations of state of dilute polymer solutions in viscoelastic fluid with one relaxation time are derived by applying a structural approach. The system under consideration is simulated by the superposition of two interpenetrating interacting conitua. The hydrodynamic behaviour of single polymer chains is simulated using the subchain model representing a linear sequence of frictional centres, spherical Brownian particles chain-bonded by means of elastic forces. The oscillatory shearing flow of the solution is studied on the basis of the equations derived. The expressions for the complex viscosity and relaxation times are determined. It is shown that the availability of polymer additions brings about a strong smearing of the relaxation spectrum of the carrying medium.     

Excluded volume effects on the birefringence and stress of dilute polymer solutions in extensional flow

An algorithm is derived for calculating flow-induced birefringence using a bead-spring model with and without excluded volume effects. The simulation results for the bead-spring model compare well with experimental results for stress and birefringence in extensional flows of dilute solutions of polystyrene molecular weight 2 million in a filament-stretching device in both “theta” and “good” solvents (Orr and Sridhar 1999; Sridhar et al. 2000). In a “good” solvent, both stress and birefringence rise much more rapidly with strain than in a “theta” solvent, making extensional rheology a very sensitive indicator of solvent quality. Received: 7 December 1999 Accepted: 23 May 2000     

On the extensional viscosity of mobile polymer solutions

We describe experimental results on the extensional viscosity of mobile polymer solutions obtained from two instruments, the first being a commercial Spin Line Rheometer and the second a custom-built lubricated-die Converging Flow Rheometer. The interpretation of data in terms of Trouton ratios is facilitated by a simple analysis for the Generalized Newtonian Fluid model.Agreement between data from the two rheometers is satisfactory and we show that polymer solutions can be either tension stiffening or tension thinning. However, the Trouton ratios in both cases are greater than the Newtonian values and we anticipate that this will always be the case for polymer solutions.Invited paper, presented at the 2nd Conference of European Rheologists, Prague, June 17–20, 1986     

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.     

Transient deformation of an inviscid inclusion in a viscoelastic extensional flow

The transient deformation of a bubble in a viscoelastic extentional flow is analyzed by means of a finite element algorithm for viscoelastic moving boundary problems. Using the Oldroyd-B constitutive model, we find that bubbles in a viscoelastic fluid deform to the same steady-state configurations as bubbles in a Newtonian fluid at equal values of the far-field extensional stresses (corresponding to different stretch rates). Vapor bubbles in a developed extensional flow collapse more readily in the viscoelastic liquid than bubbles in Newtonian fluids because of the large compressive stresses associated with the viscoelastic liquid.     

On the use of flow through a contraction in estimating the extensional viscosity of mobile polymer solutions

We consider the use of pressure measurements in contraction flows in the determination of the extensional viscosity behaviour of polymer solutions. The experimental data are interpreted on the basis of the recent theory of Binding. The resulting extensional viscosities are compared with those obtained from a commercial Spin Line Rheometer.We conclude that contraction flows provide a convenient means of determining the extensional viscosity of shear-thinning polymer solutions. The case is not so clear for constant viscosity Boger fluids.In the course of the experiments, it is shown that excess pressure losses in the contractions can be brought about by two distinct flow mechanisms in the case of Boger fluids. In the axisymmetric case, both vortex enhancement and excess pressure loss are observed, although there is not a strict one-to-one correlation between these phenomena. In the planar case, vortex enhancement is not conspicuously present, although there is still a substantial excess pressure loss at high flow rates. This excess must be associated with the ‘bulb’ flow field which essentially replaces the vortex-enhancement regime of the axisymmetric case.     

Response of viscoelastic fluids in extensional flow generated by a pulsating sphere

A simple analysis of the periodic extensional flow generated by a pulsating sphere in an infinite sea of viscoelastic fluid has been carried out. The general procedure is illustrated by two specific constitutive equations: the corotational Jeffreys fluid and the Oldroyd fluid model B. The response of these fluids is reflected in the temporal variation of the pressure on the surface of the sphere, with Reynolds and Deborah numbers and parameters of the constitutive equations as independent variables. For the case of pulsation with infinitesimal amplitude the fluid response is summarised in the form of pressure amplitude and phase lag versus Deborah number plots. The role of the pulsating flow in the characterisation of viscoelastic fluids and the extension of the procedure to other constitutive equations are briefly discussed.     

The rheology of polymer solution elastic strands in extensional flow

We apply micro-oscillatory cross-slot extensional flow to a semi-dilute poly(ethylene oxide) solution. Micro-particle image velocimetry (μPIV) is used to probe the real local flow field. Extreme flow perturbation is observed, where birefringent strands of extended polymer originate from the stagnation point. This coincides with a large increase in the extensional viscosity. The combination of stagnation point flow and μPIV enables us to investigate directly the stress and strain rates in the strand and so determine the true extensional viscosity of the localised strand alone. The Trouton ratio in the strand is found to be ~4000, amongst the highest values of Trouton ratio ever reported. Consideration of the flow in the exit channels surrounding the highly elastic strand suggests a maximum limit for the pressure drop across the device and the apparent extensional viscosity. This has implications for the understanding of high Deborah number extensional thinning reported in other stagnation point flow situations.     

Laminar axisymmetric flow of a weakly compressible viscoelastic fluid

The combined effects of weak compressibility and viscoelasticity in steady, isothermal, laminar axisymmetric Poiseuille flow are investigated. Viscoelasticity is taken into account by employing the Oldroyd-B constitutive model. The fluid is assumed to be weakly compressible with a density that varies linearly with pressure. The flow problem is solved using a regular perturbation scheme in terms of the dimensionless isothermal compressibility parameter. The sequence of partial differential equations resulting from the perturbation procedure is solved analytically up to second order. The two-dimensional solution reveals the effects of compressibility and the other dimensionless numbers and parameters in the flow. Expressions for the average pressure drop, the volumetric flow rate, the total axial stress, as well as for the skin friction factor are also derived and discussed. The validity of other techniques used to obtain approximate solutions of weakly compressible flows is also discussed in conjunction with the present results.     

The relaxation of concentrated polymer solutions

The focus of this paper is on the viscoelastic properties of concentrated polymer solutions and polymer melts. Dynamic mechanical measurements were performed on various polystyrene/ethylbenzene solutions with polymer concentrations ranging from 40% up to 100% and temperatures from Tg+30°C up to 70°C (230°C for polymer melts). The basis polymers are two commerical grade polystyrenes (BASF) with M _W = 247 kg/mol and 374 kg/mol, respectively. To avoid solvent loss due to evaporating during the measurements, a special sealing technique was used.A phenomenological model which describes quantitatively the relaxation spectrum of concentrated polymer solutions from the flow regime up to the glass transition regime is developed. The relaxation data of the respective polymer melt and the glass transition temperature of the solution are the only input parameters needed. The temperature dependence is described by a universal, concentration invariant WLF-equation. The relaxation spectra are divided into two parts accounting for the entanglement and the segmental relaxation modes, respectively. The relaxation strength related to the flow and entanglement regime scale with c ^2.3, whereas the segmental relaxation strength does not alter with concentration. All relaxation times change with concentration proportional to c ^3.5. Flow curves can be calculated from these relaxation spectra and thus, our results are useful for engineering applications.Roman Symbols a _T Time temperature superposition shift - factor - a _c Time concentration superposition - shift factor in the flow regime - a _c Time concentration superposition - shift factor in the glassy regime - b _T Modulus temperature superposition - shift factor - b _c Modulus concentration shift factor - in the flow regime - b _c Modulus concentration shift factor - in the glassy regime - B Virial coefficients - c Polymer mass fraction kg/kg - c ₁ WLF-parameter - c2 WLF-parameter K - g Relaxation strength of a relaxation Pa mode - G(t) Relaxation modulus Pa - G Storage modulus Pa - G Loss modulus Pa - GN Plateau modulus of linear flexible Pa polymers - (x) Delta function: (0) = 1, - (x<>0)=0 - h() Damping function - H() Relaxation spectrum Pa - J ₀ ^N Recoverable compliance Pa^–1 - m Mass kg - M _c Critical molecular weight kg/mol - M _e Entanglement molecular weight kg/mol - M _w Weight average molecular weight kg/mol - M Number of datapoints - n Scaling exponent - N Number of discrete relaxation modes - T Temperature °C - T _g Glass transition temperature °C - V Volume 1 Greek Symbols Scaling exponent - _f Thermal expansion coefficient K^–1 - Scaling exponent - Shear deformation - Shear rate s^t–1 - Relaxation time s - _c Characteristic relaxation time of thes Cross model - _e Entanglement relaxation time s - Viscosity Pa s - ₀ Zero shear viscosity Pa s - ₀ First normal stress coefficientPa s2 - Segmental friction coefficient - Frequency rad/s Indices f Flow and entanglement regime - g Glass transition regime - i Count parameter - p Polymer - ref Reference state - s Solvent Dedicated to Prof. Dr. J. Meissner on the occasion of his retirement from the chair of Polymer Physics at the Eidgenössische Technische Hochschule (ETH) Zürich, Switzerland     

Measurement of pressure loss in the flow of polymer solutions through wavy channels

In order to examine the flow behavior of polymer solutions through porous media, the measurement of pressure loss and the experiment for flow visualization were carried out with wavy channels as one of the model channels of porous media. The test fluids used are aqueous solutions of polyacrylamide (PAA) with two different concentrations. The occurrence of the excess pressure loss, which was not due to the effect of the centrifugal force, was found for the PAA solutions. The relations between the friction factor ratio and the Deborah number were similar to that obtained for the flow through porous media. Furthermore, the results of the flow visualization suggest that the elongational property of the PAA solutions is connected with the occurrence of the excess pressure loss.     

The unraveling of a polymer chain in a strong extensional flow

By assuming that in a strong extensional flow a polymer molecule in dilute solution is quickly driven into a folded or kinked state in which drag and entropic elastic forces dominate over the Brownian force, we derive kink dynamics equations that describe the unraveling of the molecule in the extensional flow. Solving these equations numerically, we find that although the ends of the chain move, on average, affinely in the flow field until the chain is unfolded to about 1/3 of its fully extended length, large viscous stresses are produced because the solvent must flow around nonextending strands of polymer that lie between neighboring kinks. These predictions are compared with available experimental data and with other theoretical models.     

A convective weakly viscoelastic rotating flow with pressure Neumann condition

The objective of this work is to investigate through the numeric simulation, the effects of the weakly viscoelastic flow within a rotating rectangular duct subject to a buoyancy force due to the heating of one of the walls of the duct. A direct velocity–pressure algorithm in primitive variables with a Neumann condition for the pressure is employed. The spatial discretization is made with finite central differences on a staggered grid. The pressure field is directly updated without any iteration. Numerical simulations were done for several Weissemberg numbers (We) and Grashof numbers (Gr) . The numerical results show that for high Weissemberg numbers (We>7.4 × 10^?5) and for ducts with aspect ratio 2:1 and 8:1, the secondary flow is restabilized with a stretched double vortex configuration. It is also observed that when the Grashof number is increased (Gr>17 × 10^?4) , the buoyancy force neutralizes the effects of the Coriolis force for ducts with aspect ratio 8:1. Copyright © 2008 John Wiley & Sons, Ltd.     

Brownian dynamics simulations of star-branched polymers in dilute solutions in extensional flow

Using Brownian dynamics (BD) simulations of FENE bead-spring models, the dynamics of star-branched polymers in dilute solutions under extensional flow have been investigated. Studies on star polymers in transient extensional flow reveal that the initial transient stress response at low strains is governed by both the number of arms and the shortest arm. On the other hand, the steady-state behavior of star polymers in elongational flow is limited by the maximum effective “contour” length of the molecules. The distribution of arm extension and birefringence of the star-branched molecule are broader and the mean is shifted to lower values, when compared to equivalent linear systems. As a result, the degree of arm extension at steady-state decreases as the number of arms in the star increases. Both an analysis of individual ensembles in Brownian dynamics simulations and a study of a simple force balance indicate that the constraint imposed on the star arms by the central branch point and contributions from “asymmetric” arm arrangements give rise to overall less extended and oriented star-branched molecules with broader arm extension and birefringence distributions. The results obtained from stress-conformation hysteresis simulation indicate that less-stretched arms exhibit more retarded relaxation, as the number of arms increases in star-branched molecules. The effect of excluded volume (EV) interactions, incorporated through the Lennard–Jones potential, on the dynamics of star polymers in extensional flow appears unimportant.