Semi-empirical theory of the viscosity of moderately dilute polymer solutions

The viscosity of moderately dilute polymer solutions is formulated on the postulates that in this concentration region is governed by the domain volume per polymer segment and the noddle effect due to entangling chains. The former is treated semi-molecular theoretically, and the latter entirely phenomenologically. All the parameters involved in the theory can be estimated from appropriate dilute solution data as well as the asymptotic molecular-weight dependence of at different concentrations. It is shown that the theory describes almost quantitatively the experimental data obtained by Hamada and Adam and Delsanti for polystyrene in benzene and cyclohexane. Part of these data reveals the breakdown of the semidilute solution approximation used in the theory.     

Measurement of dynamic properties of dilute polymer solutions with a Laser-Doppler velocimeter

The complex velocity field of an oscillating Couette flow is measured with a Laser-Doppler velocimeter. Different evaluation methods are used for the determination of material functions such as relaxation times and the dynamic complex viscosity.     

Quantitative description of rheological properties of dilute polymer solutions

The Rouse-Zimm model has been generalized to describe the rheology of dilute polymer solutions at moderate shear rates by allowing for a reduced-shear-rate dependent slippage of the carrier solvent in the neighbourhood of the polymer coil with respect to the macroscopic continuum. A comparison of the theoretical predictions with published viscosity data for monodisperse polymer systems shows good agreement. Thus it appears to be sufficient to measure the intrinsic viscosity in order to estimate all the material functions of interest for the steady and dynamic shear flow of dilute polymer solutions.     

Hydrodynamic interactions of dilute polymer solutions under shear flow in a narrow channel

Hydrodynamic interactions on dilute solutions of spherical beads under shear flow are calculated with the method of induced forces. The Navier-Stokes equation is considered in the Stokes approximation. Hydrodynamic interactions cause the drag to be anisotropic in space.Numerical solutions are obtained for the added stress, caused by polymeric molecules in solution in a narrow channel under shear flow. The polymeric molecules are considered as Hookean spring-dumbbells.Slip velocity and the effective viscosity are obtained taking different dumbbells' bead radii. Transversal migration in the channel is obtained for different bead radii.     

Comparison of a new internal viscosity model with other constrained-connector theories of dilute polymer solution rheology

Complex viscosity ^* = -i predictions of the Dasbach-Manke-Williams (DMW) internal viscosity (IV) model for dilute polymer solutions, which employs a mathematically rigorous formulation of the IV forces, are examined in the limit of infinite IV over the full range of frequency number of submolecules N, and hydrodynamic interaction h ^*. Although the DMW model employs linear entropic spring forces, infinite IV makes the submolecules rigid by suppressing spring deformations, thereby emulating the dynamics of a freely jointed chain of rigid links. The DMW () and () predictions are in close agreement with results for true freely jointed chain models obtained by Hassager (1974) and Fixman and Kovac (1974 a, b) with far more complicated formalisms. The infinite-frequency dynamic viscosity predicted by the DMW infinite-IV model is also found to be in remarkable agreement with the calculations of Doi et al. (1975). In contrast to the other freely jointed chain models cited above, however, the DMW model yields a simple closed-form solution for complex viscosity expressed in terms of Rouse-Zimm relaxation times.     

Constitutive equation for dilute polymer solutions in strong elongational flow

A constitutive equation is proposed, which is constructed using both phenomenological and structural ideas. In this formulation, the kinematics of the fluid is characterized by the deformation rate and a structural vector. The vector follows an evolutionary law which is inspired by known molecular models. The expression for the stress is given by introducing a dissipative term related to the strong hydrodynamic interaction of the distorted molecules and a deformation term for the molecules, as well as by using the second law of thermodynamics.A study of the general properties of the evolutionary equation and its response in a homogeneous two-dimensional flow provides evidence of the performance of the proposed model.     

Effect of a controlled pre-deformation history on extensional viscosity of dilute polymer solutions

We use a modified filament stretching rheometer to quantify the influence of a known controlled pre-shear history on the transient extensional viscosity of a dilute polymer solution. Two different types of pre-deformation are explored; both influence the subsequent stretching significantly, albeit in opposite ways. Small-amplitude oscillatory straining parallel to the direction of stretching enhances strain hardening and accelerates the tensile stress growth toward the steady-state value. Conversely, steady torsional shearing orthogonal to the direction of stretching retards strain hardening and results in a delayed approach to steady-state elongational flow. In both cases, the final steady-state extensional viscosity is the same as that observed with no pre-shearing. Calculations using a finitely extensible nonlinear elastic Peterlin dumbbell model qualitatively capture the trends observed in experiments, enabling interpretation of these observations in terms of the degree of polymer chain stretching imposed by the flow before extensional stretching.     

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     

Drag of a sphere in dilute polymer solutions in high Reynolds number range

We have measured by means of four ultrasonic transducers the fall velocity of a sphere at high Reynolds number range in dilute polyacrylamide solutions which have viscoelastic effects. The polymer solutions were 5, 20 and 50ppm in the concentration. Basset-Bousinessq-Oseen equation for the falling sphere was analyzed numerically on Newtonian fluids in order to compare with the fall velocity of a sphere in the polymer solutions, and the experimental data of the fall velocity in tap water is in agreement with the range of no effect of the test tank wall. In polymer solutions, it was shown that the fall velocity is larger than that in Newtonian fluids within the critical Reynolds number range such that the drag reduction occurs and is smaller than that of Newtonian fluids over the range. The experimental data for the drag reduction ratio of polymer solutions is arranged by Weissenberg number calculating the experimental data of the first normal stress differences. It was shown that the maximum drag reduction ratio in the polymer solutions lies in the range of We=3∼10. Received: 15 October 1997 Accepted: 12 May 1998     

Rheological interpretation of pressure anomalies of aqueous dilute polymer solutions (ADPS) in orifice flow

The response of a considerable number of solutions of several polymers (PEO, HPAM, PAM) with concentrations of less than 100 ppm in orifice flow has been investigated. It is shown that the excess pressure (difference between the ADPS and the solvent total pressure drop) behaves linearly as a function of a superficial strain rate (ratio between a velocity and a length scale). In rheological terms this behaviour is interpreted as the result of a constant elongational viscosity whose values are two to three orders of magnitude larger than the shear viscosity. A formal approach to this phenomenological interpretation is suggested.     

Some thermal and rheological properties of homogeneous interpenetrating polymer networks

Summary Homogeneous interpenetrating polymer networks, (IPNs), consisting of methacrylic and epoxy networks, were obtained at various compositions from a simultaneous polymerization of DGEBAMA and DGEBA. For each composition, the glass transition occurs at a well-defined temperature which is lower than the weighted average of the glass transition temperatures of each component. Tensile experiments showed a change of mechanical behaviour above some critical strain value. This phenomenon was corroborated by stress relaxation tests which allowed the determination of a complete relaxation below a critical strain. This strain is increasing with the temperature and decreasing with the crosslink density. Such a property disappeared after the addition of grafting molecules which prevented both networks from any relative sliding. In this way this behaviour appears to be a specific property of interpenetrating networks.With 10 figures     

Formation of the shear-induced state in dilute cationic surfactant solutions

In cationic surfactant solutions a change of state occurs due to mechanical stresses. In the dilute regime of rodlike micelles the formation of a so-called Shear-Induced State (SIS) occurs above a critical shear rate. In this context dilute means that there is no sterical interaction between rodlike micelles, the solution is below the overlap concentration. Employing a mathematical model, it is shown that aggregation forces are weak compared to hydrodynamic forces. The mathematical formulation is based on a model of Israelachvili which describes the chemical potential of micelles. Hydrodynamic forces are calculated with a rigid-dumbbell model. SIS formation can be explained by the destruction of rodlike micelles.     

Effect of internal viscosity and elasticity of ellipsoidal macromolecules on the rheological behavior of dilute polymer solutions. rheological equations of state

The structural-continuum approach is used to obtain the Theological equations of state for dilute polymer solutions whose macromolecules can be modeled by an ellipsoid of rotation with internal viscosity and elasticity.Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 3, pp. 94–98, May–June, 1976.     

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.     

The charged dumbbell model for dilute polyelectrolyte solutions in strong flows

A charged dumbbell model is used to investigate the behavior of dilute polyelectrolyte solutions in a general linear two-dimensional flow. The model studied has a nonlinear spring, conformation dependent friction and a Coulombic repulsive force due to an effective electrostatic charge on the two beads. The relative importance of the electrostatic charge is reflected by an effective charge density parameter,E. Equilibrium properties such as end-to-end distance and intrinsic viscosity are strongly dependent onE. In strong flows, which produce a dramatic increase in the dumbbell dimensions (a coil-stretch transition), the onset behavior is influenced byE. IncreasingE causes the onset velocity gradient to shift to much lower values. Large values ofE change the qualitative behavior to that of rigid (or slightly extensible) macromolecules or fibers. Results are presented for a charged dumbbell at equilibrium, in steady flows, and in transient flows.