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.     

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.     

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.     

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.     

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.     

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.     

A novel geometry for rheological characterization of viscoelastic materials

A novel geometry for generating a viscometric flow presents advantages of both cone and plate and parallel plate geometries, regarding uniform shear field and adjustable range of measurement. Kinematics and dynamics of the generated flow have been described mathematically utilizing an orthogonal curvilinear coordinate system based on the shapes of the shearing surfaces which are similar to the surface that generates the flow. Simple equations that allow the calculation of quantities of experimental interest in the rheological characterization of liquid materials, namely, shear rate, shear stress and two normal stress differences, have also been derived.The geometry, called pseudosphere, was tested with two types of fluids (Newtonian and pseudoplastic). Results show that the geometry can be used with low viscosity liquids (Newtonian liquids) by only adjusting the gapH. The behavior of pseudoplastic fluids for both low and moderately high viscosity could also be studied with this geometry. Very reproducible results were obtained when compared with those obtained with cone and plate geometry. Regions of lower shear rate could be studied using only the pseudosphere geometry.     

Rubber-like elasticity by boundary element method: Finite deformation of a circular elastic slice

We briefly review the phenomenological theory of rubber-like elasticity and report a microstructural model that leads us to eventually adopt a particular constitutive equation, which includes the Neo-Hookean and the Mooney materials. A numerical implementation of the Boundary Element method for solving a general two-dimensional or axisymmetric finite deformation problem is described and tested with some simple deformations. The resulting program is used to analyse the finite deformation of a circular elastic slice perfectly bonded to two parallel rigid end plates; the bottom plate is stationary and the top plate is given a constant displacement. The problem has a free surface which must be found as part of the solution. The results indicate that the Boundary Element method can be an efficient tool for stress-strain analyses with rubber-like materials.     

Measurement of the shear viscosity using a newly developed GRLDA-viscometer

A two-point laser-Doppler anemometer is used to determine velocity gradients. Measuring additionally the pressure drop in channel flow allows one to use this instrument as a viscometer. This is demonstrated by measuring two polymer solutions as well as water. Besides the velocity gradient, the system also furnishes the velocity as well as velocity fluctuations. For surfactant solutions the sudden increase in these fluctuations go hand-in-hand with the sudden shear thickening reported. This behavior thus seems to be caused by a change in type of flow field (structural turbulence) rather than a change in the rheology of the surfactant solutions.This paper is dedicated to Professor Hanswalter Giesekus on the occasion of his retirement as Editor of Rheologica Acta.     

Stress optical measurement of the third normal stress difference in polymer melts under oscillatory shear

Results are reported for the dynamic moduli,G andG, measured mechanically, and the dynamic third normal stress difference, measured optically, of a series bidisperse linear polymer melts under oscillatory shear. Nearly monodisperse hydrogenated polyisoprenes of molecular weights 53000 and 370000 were used to prepare blends with a volume fraction of long polymer, _L, of 0.10, 0.20, 0.30, 0.50, and 0.75. The results demonstrate the applicability of birefringence measurements to solve the longstanding problem of measuring the third normal stress difference in oscillatory flow. The relationship between the third normal stress difference and the shear stress observed for these entangled polymer melts is in agreement with a widely predicted constitutive relationship: the relationship between the first normal stress difference and the shear stress is that of a simple fluid, and the second normal stress difference is proportional to the first. These results demonstrate the potential use of 1,3-birefringence to measure the third normal stress difference in oscillatory flow. Further, the general constitutive equation supported by the present results may be used to determine the dynamic moduli from the measured third normal stress difference in small amplitude oscillatory shear. Directions for future research, including the use of birefringence measurements to determineN ₂/N ₁ in oscillatory shear, are described.     

Rheological characteristics of sewage sludge: A granuloviscous material

Problems have been experienced in the screw conveying of a centrifuge dewatered sewage sludge, at about 66% by weight water content. The rheology of the sludge was therefore tested in a viscometer in which the normal stress between the platens could be controlled. Rough platens were used to measure internal shear strengths while smooth steel platens were used to study wall slip.The sludge displayed a number of the characteristics of a granuloviscous material. It was found to possess high initial shear strength, but rapidly softened with shear to lower steady-state strengths. The initial shear strength increased with increasing normal stress, indicating that the sludge was frictional. The initial strength was lower against the smooth platen.The steady-state shear strengths were both rate and stress dependent using the rough platen, and this internal shear strength could be described by a frictional pseudoplastic equation. Using the smooth platen the material was nearly rate independent, and was best described by a Coulomb friction equation. At the higher rates the wall shear strengths were lower than the internal shear strengths.The strengths (both initial and steady-state) were characterised by a high degree of variability from sample to sample, and also showed marked hysteresis with the rough platen. They did not show any consistent variation with moisture content.In terms of screw conveying, the major conclusion is that smooth walls to the flights of the screw and barrel of the conveyor are desirable.     

The influence of surface friction on the calculation of stress relaxation parameters for processed cheese

The stress relaxation-time behaviour of processed cheese has been studied after compression by 5–20%. Data were corrected for surface friction effects, since it is only that part of the registered force which actually compresses the samples that relaxes exponentially. The method of successive residuals and an empirical normalization linearization procedures were used to analyse the data. In both cases it was found that several of the calculated rheological parameters, at any selected compression, were significantly higher after correcting for surface friction. The initial compression also influenced the magnitude of the rheological parameters.     

An experimental study of exit pressures for polymer melts

A slit die apparatus is used to measure exit pressures for five different polymer melts. Viscosity data obtained from the same apparatus agree well with values obtained from a cone-and-plate rheometer or a capillary rheometer. Except for a PVC sample where thermal degradation was found to occur, the exit pressures obtained by linear extrapolation of the measured pressure profiles are all positive, and increase with increasing shear stress. The values of the first normal stress difference calculated according to the exit pressure theory are of the right order of magnitude and in some cases correlate satisfactorily with values measured in a cone-and-plate rheometer. However, the high sensitivity of the exit pressure values to the method of extrapolation and the wild scatter of exit pressure data for some materials make it difficult to use the exit pressure method as a routine procedure for accurate determination of the first normal stress difference.     

An adaptation of finite linear viscoelasticity theory for rubber-like viscoelasticity by use of a generalized strain measure

In this paper a simplified three-dimensional constitutive equation for viscoelastic rubber-like solids is derived by employing a generalized strain measure and an asymptotic expansion similar to that used by Coleman and Noll (1961) in their derivation of finite linear viscoelasticity (FLV) theory. The first term of the expansion represents exactly the time and strain separability relaxation behavior exhibited by certain soft polymers in the rubbery state and in the transition zone between the glassy and rubbery states. The relaxation spectra of such polymers are said to be deformation independent. Retention of higher order terms of the asymptotic expansion is recommended for treating deformation dependent spectra.Certain assumptions for the solid theory are relaxed in order to obtain a constitutive equation for uncross-linked liquid materials which exhibit large elastic recovery properties.Apart from the strain energyW(I₁,I ₂), which alternatively characterizes the long-time elastic response of solids or the instantaneous elastic response of elastic liquids, only the linear viscoelastic relaxation modulus is required for the first-order theory. Both types of material functions can be obtained, in theory, from simple laboratory testing procedures. The constitutive equations for solids proposed by Chang, Bloch and Tschoegl (1976) and a special form of K-BKZ theory for elastic liquids are shown to be particular cases of the first-order theory.Previously published experimental data on a cross-linked styrene-butadiene rubber (SBR) and an uncross-linked polyisobutylene (PIB) rubber is used to corroborate the 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.     

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.     

Nonlinear viscoelasticity of polymer melts in different types of flow

The nonlinear viscoelastic properties of a fairly large class of polymeric fluids can be described with the factorable single integral constitutive equation. For this class of fluids, a connection between the rheological behaviour in different flow geometries can be defined if the strain tensor (or the damping function) is expressed as a function of the invariants of a tensor which describes the macroscopic strain, such as the Finger tensor. A number of these expressions, proposed in the literature, are tested on the basis of the measuring data for a low-density polyethylene melt. In the factorable BKZ constitutive equation the strain-energy function must be expressed as a function of the invariants of the Finger tensor. The paper demonstrates that the strain-energy function can be calculated from the simple shear and simple elongation strain measures, if it is assumed to be of the shape proposed by Valanis and Landel. The measuring data for the LDPE melt indicate that the Valanis-Landel hypothesis concerning the shape of the strainenergy function is probably not valid for polymer melts.