Comparison of the rheology of polymer melts in shear,and biaxial and uniaxial extensions

The experimental properties of different polymer melts, polystyrene, high density polyethylene and low density polyethylene are compared for the first time in three different deformations: step shear, step biaxial extension and steady uniaxial extension. Properties of three other melts are also studied in step biaxial and shear experiments. For our comparative purposes some data of Laun and Winter from the literature are used, as well as new data reported here. In all the step strain experiments, the stresses can be factored into a time dependent relaxation modulus and a strain dependent damping function. The data are interpreted using a differential constitutive equation of Larson which satisfies this time-strain separability and has a single parameter that describes the strain softening character of the material. Results show that differences in the properties of the melts are most pronounced in uniaxial extension and least in biaxial extension. All melts follow the Doi-Edwards prediction relatively closely in biaxial extension. In uniaxial extension, the branched material shows a strong strain hardening effect although its shear and biaxial properties are similar to the other melts. The constitutive model gives a reasonably good fit to the data in all three deformations for unbranched materials for the same value of the adjustable parameter; the model, however, fails for the branched low density polyethylene.     

Non Linear Rheology for Long Chain Branching characterization,comparison of two methodologies : Fourier Transform Rheology and Relaxation.

In this study we compare three rheological ways for Long Chain Branching (LCB) characterization of a broad variety of linear and branched polyethylene compounds. One method is based on dynamical spectrometry in the linear domain and uses the van Gurp Palmen plot. The two other methods are both based on non linear rheology (Fourier Transform Rheology (FTR) and chain orientation/relaxation experiments). FTR consists in the Fourier analysis of the shear stress signal due to large oscillatory shear strains. In the present work we focus on the third and the fifth harmonics of the shear stress response. Chain orientation/relaxation experiment consists in the analysis of the polymer relaxation after a large step strain obtained by squeeze flow. In this method, relaxation is measured by dynamical spectrometry and is characterized by two relaxation times related to LCB. All methods distinguish clearly the group of linear polyethylene from the group of branched polyethylene. However, FTR and Chain orientation/relaxation experiments show a better sensitivity than the van Gurp Palmen plot. Non linear experiments seem suitable to distinguish long branched polyethylene between themselves.     

Stress relaxation after a step strain in uniaxial extension of polyisobutylene and polyethylene

The morphology of molten polymeric materials is known to be less sensitive to shear than to extensional deformations. However, it is not easy to characterise molten polymeric materials in simple extensional flows due to the large number of experimental difficulties involved. This has led to the effective absence of a structure-preserving, morphology probing technique similar to the ones commonly found in shear, i.e., the equivalent of stress relaxation and oscillatory experiments. It is the aim of the present work to demonstrate the usefulness of a recently developed experimental technique that enables stress relaxation experiments after a step strain in uniaxial extension to be performed. Results are presented for two model melts (polyisobutylene, PIB, of different molecular weights) and for a series of linear low-density polyethylenes, LLDPE, in which the molecular structure (molecular weight, MW, molecular weight distribution, MWD and degree of long chain branching, LCB) is changed systematically. It is shown that, for both types of materials, stress relaxation experiments in extension yield quantitatively correct results and that this technique is more sensitive to differences in molecular structure than oscillatory experiments in shear.     

Transient shear flow properties of fiber-filled polyethylene melts

The growth and relaxation of shear and normal stresses have been investigated for glass and carbon fiber-filled polyethylene melts over a wide range of shear rates and temperatures by means of a cone-and-plate rheogoniometer. Flow parameters and flow curves characterizing the stress overshoot and relaxation phenomena of the fiber-filled systems were determined experimentally. The influence of fiber loading, fiber size and temperature on the transient flow parameters are discussed.Predictions by the Meister and Bogue constitutive equations were compared with the experimental data for the transient shear and normal stresses. These equations predict satisfactorily the non-linear transient shear flow of polymer melts and its fiber-filled systems.     

Simulation of the linear rheological behavior of silica-filled,star-shaped SBR compounds

The rheological behavior of star-shaped SSBR/silica 60 phr compounds with different filler surface areas was experimentally studied and simulated using constitutive modeling. Rheological behavior was characterized in small amplitude oscillatory shear (SAOS) and stress relaxation after a small step shear. Unfilled SBR and SBR filled with four different silica grades with BET surface areas of 55, 135, 160, and 195 m²/g were used. A clear trend in rheological behavior was observed with surface area. A frequency sweep in the SAOS regime indicated an increase in dynamic properties with surface area. Additionally, linear stress relaxation tests at a strain level of 0.05 showed an increase in relaxation modulus with surface area and the presence of a plateau in the relaxation modulus at large times in compounds containing silica with high surface areas. The Leonov and Simhambhatla-Leonov models, modified to incorporate multimode particle network relaxation, were successfully used to simulate the frequency dependence of the storage modulus and the time evolution of the linear relaxation modulus for all samples. However, simulations of the frequency dependence of the loss modulus showed poor results in comparison with experimental data for the filled compounds.     

Prediction of multiple overshoots in shear stress during fast flows of bidisperse polymer melts

We present a differential constitutive model of stress relaxation in polydisperse linear polymer melts and solutions that contains contributions from reptation, contour-length fluctuations, and chain stretching. The predictions of the model during fast start-up and steady shear flows of polymer melts are in accord with experimental observations. Moreover, in accordance with reported experimental literature (Osaki et al. in J Polym Sci B Polym Phys 38:2043–2050, 2000), the model predicts, for a range of shear rates, two overshoots in shear stress during start-up of steady shear flows of bidisperse polymer melts having components with widely separated molar masses. Two overshoots result only when the stretch or Rouse relaxation time of the higher molar mass component is longer than the terminal relaxation time of the lower molar mass component. The “first overshoot” is the first to appear with increasing shear rate and occurs as a result of the stretching of longer chains. Transient stretching of the short chains is responsible for the early time second overshoot. The model predictions in steady and transitional extensional flows are also remarkable for both monodisperse and bidisperse polymer solutions. The computationally efficient differential model can be used to predict rheology of commercial polydisperse polymer melts and solutions.     

Evaluation by means of stress relaxation (after a step strain) experiments of the viscoelastic behavior of polymer melts in uniaxial extension

 As is widely acknowledged, morphology in most materials is far more sensitive to extensional than to shear deformations but, unfortunately, due to the experimental difficulties involved, there are no non-destructive, morphology probing techniques in such flows, i.e., the equivalent of stress relaxation and oscillatory experiments in shear flows. This paper tries to overcome some of those drawbacks by proposing an experimental technique that allows stress relaxation experiments after a step strain in uniaxial extension to be performed. The benefits of this technique are twofold: (a) while the deformation is small enough for the response to be in the linear viscoelastic regime it constitutes a probe of the microstructure of the material and (b) it allows the departure to the non-linear regime to be studied, useful, for example, for the definition of the damping function in uniaxial extensional flow or for the study of the response of materials to fast transient flows with a strong extensional component, such as contraction flows. In this work the proposed technique, which requires a correction to the apparent (theoretical) strain rate in order to allow the calculation of the true Hencky strains attained during the strain step, is tested and validated for two polyisobutylene melts. Received: 9 April 2001 Accepted: 26 July 2001     

Viscoelastic plastic rheological model for particle filled polymer melts

A viscoelastic plastic model for suspension of small particles in polymer melts has been developed. In this model, the total stress is assumed to be the sum of stress in the polymer matrix and the filler network. A nonlinear viscoelastic model along with a yield criterion were used to represent the stresses in the polymer matrix and the filler network, respectively. The yield function is defined in terms of differential equations with an internal parameter. The internal parameter models the evolution of structure changes during floc rupture and restoration. The theoretical results were obtained for steady and oscillatory shear flow and compared with experimental data for particle filled thermoplastic melt. The experimental data included the steady state shear strress over a wide range of shear rates, the transient stress in a start up shear flow, stress relaxation after cessation of a steady state shear flow, the step shear and the oscillatory shear flow at various amplitudes.     

Dynamic and transient rheological properties of glass filled polymer melts

The dynamic and transient rheological properties of a low density polyethylene melt and a plasticized polyvinylchloride melt filled with glass beads were measured at 200 °C and 180 °C respectively in a modified Weissenberg Rheogoniometer R-17. Its main modification consisted of the use of a piezoelectric transducer instead of the conventional torsion bar, and of the interfacing of a microcomputer Apple II plus to the Rheogoniometer for data acquisition and analysis. The glass beads were pretreated with silane and titanate coupling agents to observe the effect of the chemical modification of the polymer filler interface on these properties. It was observed that both the dynamic viscosity and the storage modulus increased with the weight fraction, but this last parameter did appreciably affect the stress growth and stress relaxation curves of the polymeric matrices at low shear rates. The effect of coupling agents on these properties was varied.     

Review of the entry flow problem: Experimental and numerical

This paper is concerned with a review of both experimental and numerical studies of axisymmetric and planar entry flows which have been considered as test problems for the numerical simulation of viscoelastic fluids. The test of the method is usually based upon whether the numerical model predicts vortices in the entry corners. However, it is not clear as to whether one should observe vortices for all viscoelastic fluids. Polyacrylamide solutions and Boger fluids exhibit vortices in axisymmetric flow and the size of the vortex does increase with fluid elasticity. However, the vortex is nearly suppressed in planar entry flow. On the other hand, not all polymer melts are found to exhibit vortices in either axisymmetric or planar entry flow. It is our belief that the origin of vortices is not related to the elasticity based on shear flow propertes but to the behavior of the transient extensional viscosity. Certain polymer melts such as low density polyethylene exhibit vortices in both planar and axisymmetric flow along with unbounded stress growth at the start up of extensional flow. It is believed that the constitutive equations used in the numerical simulation must reflect this extensional behavior if vortices are to be predicted. A review of the numerical simulations concerned with entry flow shows that there is considerable doubt about the accuracy of the predictions for most of the studies. Even for those where the numerical solution is thought to be accurate, the magnitude of the stream function associated with the vortices is usually very low. None of the differential models used to date predicts strain hardening extensional viscosity, but those which are thought to predict vortices do rise more rapidly to the steady-state extensional viscosity values with time. It is recommended that the search of test fluids be widened beyond polymer solutions as there may already exist a number of polymer melts which behave similarly to the predictions of existing constitutive equations.     

Constitutive relationships for polymeric materials with power-law distributions of relaxation times

The linear relaxation modulus of polydisperse polymer melts and solutions can often be approximated by a power law,ct ^–m over some range of time,t. If, in addition, the nonlinear rheology is given by a separable integral equation, with a strain-dependent factor typical of those observed experimentally, then some commonly observed empirical rules and equations can be readily derived as approximations, namely the Cox-Merz relationship between complex viscosity and steady-state shear viscosity, Bersted's predictions of steady shear stress and first normal-stress difference from a truncated spectrum of linear relaxation times, and the observation of Koyama and coworkers that the ratio of the nonlinear to the linear time-dependent elongational viscosity is independent of strain rate, over a range of strain rates outside the linear regime.     

Large-amplitude oscillatory shear flow from the corotational Maxwell model

Using the single relaxation time corotational Maxwell fluid, we derive explicit analytical expressions for the first, third, and fifth harmonics of the alternating shear stress response in large-amplitude oscillatory shear (LAOS). We also derive corresponding expressions for the zeroth, second, and fourth harmonics of both the first and second normal stress differences. These harmonics are found to depend upon just two dimensionless groups: the Deborah and Weissenberg numbers, each of which causes non-Newtonian behavior. The form of the solution for the corotational Maxwell model in LAOS matches the forms of the analytical solutions for two molecular models for dilute solutions and one for concentrated solutions or melts. We also derive an analytical solution for the corotational Maxwell model after startup of LAOS. For this we find that both small and large amplitude cases approach a periodic limit cycle (alternance) at the same rate for both the shear stress response and for the normal stress differences. For molten high density polyethylene that is lightly filled with carbon black, we find good quantitative agreement with measured LAOS behavior when our analytical solution is superposed for multiple relaxation times.     

Exponential shear flow of branched polyethylenes in rotational parallel-plate geometry

Exponential shear flow, as a strong flow with the potential to generate a high degree of molecular stretching, has attracted considerable interest in recent years. So far, exponential shear flow has been realized by either sliding-plate or cone-and-plate (CP) geometry. Both geometries guarantee homogeneous shear flow. Here, we present experimental data on exponential shear flow of several long-chain branched polyethylene melts with different degrees of strain hardening obtained by using parallel-plate (PP) geometry in a rotational rheometer. This type of geometry, which is standard in linear-viscoelastic characterization of polymer materials, produces inhomogeneous shear flow. A comparison of exponential shear flow data obtained by PP and CP geometry is made. Additionally, the experimental data are compared to predictions of the rubber-like liquid (RLL) and the molecular stress function (MSF) theories. For this purpose, the relaxation spectra of the polymer melts considered were obtained by standard linear-viscoelastic characterization. In addition, two irrotational parameters and one rotational parameter are required by the MSF theory. While the irrotational parameters were obtained from fitting to elongational viscosity data, the value of the rotational parameter was used as given in the literature. It can be concluded that viable experimental data in exponential shear flow can be obtained by PP geometry. For finite linear-viscoelasticity (RLL theory), predictions of reduced shear stress for CP and PP geometry coincide, but nonlinear material behavior (as modeled by the MSF theory) leads to small differences between both geometries. Furthermore, it is shown that the MSF predictions are in excellent agreement with the experimental data in exponential shear flow and that this type of flow leads to much less chain stretching than elongational flow.Dedicated to the memory of Prof. Arthur S. Lodge (1922–2005).     

The strain-hardening behaviour of linear and long-chain-branched polyolefin melts in extensional flows

By generalizing the Doi-Edwards model to the Molecular Stress Function theory of Wagner and Schaeffer, the extensional viscosities of polyolefin melts in uniaxial, equibiaxial and planar constant strain-rate experiments starting from the isotropic state can be described quantitatively. While the strain hardening of four linear polymer melts (two high-density polyethylenes, a polystyrene and a polypropylene) can be accounted for by a tube diameter that decreases affinely with the average stretch, the two long-chain-branched polymer melts considered (a low-density polyethylene and a long-chain branched polypropylene) show enhanced strain hardening in extensional flows due to the presence of long-chain branches. This can be quantified by a molecular stress function, the square of which is quadratic in the average stretch and which follows from the junction fluctuation theory of Flory. The ultimate magnitude of the strain-hardening effect is governed by a maximum value of the molecular stress, which is specific to the polymer melt considered and which is the only free non-linear parameter of the theory. Received: 1 June 1999/Accepted: 24 November 1999     

Relaxation effects of slip in shear flow of linear molten polymers

The transient shear response of a linear molten polymer (linear low-density polyethylene) in the nonlinear domain was studied using a true shear (sliding plate) rheometer with different gap spacings to detect slip effects. It was found that nonlinear viscoelasticity is further complicated by wall slip phenomena. Experimental evidence suggested that static slip models coupled with Wagner’s constitutive equation cannot adequately describe the experimental data at large and fast shear deformations. A new dynamic slip model involving multiple slip relaxation times is proposed in this paper, together with a method to assess the model parameters. Significant improvement in predicting the stress response is demonstrated by several examples of start-up of steady shear and large-amplitude oscillatory tests of a linear low-density polyethylene.     

Relaxation time spectra of star polymers

 The linear viscoelastic data for model star polymer melts with varying functionality and arm molecular weight were represented by means of a modified Baumgaertel-Schausberger-Winter (BSW) relaxation time spectrum, based on data analysis with the parsimonius model of Baumgaertel et al., reported in 1990. In the case of high arm functionality, the second slow terminal relaxation observed by Vlassopoulos et al. in 1997, was captured with a straightforward extension of the BSW model using broad cut-off functions. This study represents a potentially promising attempt to extend the applicability of this representation of viscoelastic data to more complex architectures, beyond simple linear chains which are characterized by self-similarity. The casting of linear viscoelastic data into spectra allows the exploration of star polymer behavior. It is a necessary step in preparation for large scale complex flow calculations in conjunction with constitutive models and for material databases. Received: 18 November 1998/Accepted: 12 August 1999     

An experimental study of food melt rheology

The shear viscosity of commercial maize grits, potato powder and a low density polyethylene has been measured under a range of extrusion processing conditions using an extruder-fed slit die viscometer and a capillary rheometer. The results show the strong dependence of the viscosity of food melts on the processing history undergone during extrusion. To this end, the shear viscosity data for the food materials have been fitted to relationships including the effects of temperature, shear rate and moisture. The effect of the shear processing history on the viscosity has been represented by a power-law relationship with extruder screw speed.     

Stress relaxation after oscillatory shear in a thermotropic liquid crystalline polymer

We report investigations of the rheology of a thermotropic liquid crystalline polymer subjected to oscillatory shear. In particular, we have studied its stress relaxation behaviour and found it to be well-represented by the linear viscoelastic model. In our studies, we observed a strong dependence of the relaxation rate on the position in the strain cycle at which the shear is stopped; a result which we show to be a general phenomenon of viscoelastic fluids and not unique to liquid crystalline polymers.     

A linear viscoelastic model for solid polyethylene

Stress relaxation tests have been carried out on a blue, pipe grade PE 80 medium density polyethylene (BP Chemicals), to provide thermo-viscoelastic rheology for use in calculating thermal stresses in pipe production. Stresses up to 4 MPa were used, with strains up to about 2%, in tests at temperatures from 23° to 90°C. Within this range a linear viscoelastic model was applicable, provided the initial ramp strain rate was less than 7×10^–5 s^–1. The stress relaxation data was fitted directly by a model incorporating an elastic response to volumetric strains, and a generalised linear solid model, consisting of two Maxwell elements and a purely elastic element in parallel, for deviatoric strains. Arrhenius type temperature dependence of relaxation times and shear moduli is found, and within experimental accuracy the temperature dependence of all these model parameters is the same. As a consequence, and provided that the duration of the strain ramp is sufficiently short relative to relaxation times, the model leads to time-temperature superposition of the relaxation moduli, using the same shift factor on both the response magnitude and time axes.