Prediction of steady-state viscous and elastic properties of polyolefin melts in shear and elongation

The linear and nonlinear steady-state viscosities and elastic compliances were measured in shear and elongational flows for two low-density polyethylenes, a linear polypropylene, and two metallocene catalyzed polyethylenes (one linear and one long-chain branched) by Wolff et al. (Rheol Acta 49:95?C103, 2010) and Resch (dissertation, 2010). Comprehensive data of this type are rarely found in the literature, and comprehensive modeling of both viscous and elastic effects is even rarer. In this contribution, the reliability of a modeling approach proposed by Laun (J Rheol 30(3):459?C501, 1986) and based on the damping function concept is tested. The strain hardening seen for the long-chain branched polymers and its absence in the case of the linear polymer, the stronger decrease of the tensile compliance in comparison to the shear compliance with increasing stress, as well as the extended linear-viscoelastic regime of the shear viscosity in contrast to the shear compliance are correctly modeled. While the modeling of the nonlinear response in shear can be achieved with only one material parameter for most of the polymers considered here, the nonlinear modeling in elongation is achieved with two parameters. The same parameter values are shown to describe viscous as well as elastic properties of the melts, and thus the relations of Laun can be used to test the consistency of viscosity and compliance measurements.     

Elongational properties and molecular structure of polyethylene melts

Summary The viscosity and the recoverable strain in the steady state of elongation have been measured on several polyethylenes of different molecular structures. The elongational viscosity as a function of tensile stress runs through a more or less pronounced maximum in the nonlinear range whereas in the linear range the Trouton viscosity is reached. For low density polyethylenes it could be demonstrated that the maximum of the steady-state elongational viscosity and the elasticity expressed by the steady-state compliances in shear and tension sensitively increase if the molecular weight distribution is broadened by the addition of high molecular weight components. A variation of the weight average molecular weight does only shift the elongational viscosity curve but leaves its shape unchanged. Two of the four high density polyethylenes investigated do not show a maximum of the steady-state elongational viscosity, for the others it is less pronounced than in the case of low density polyethylenes. The influence of branching on the elongational behaviour of polyethylene melts in the steady-state and the transient region is qualitatively discussed.With 11 figures and 4 tables     

Rheological properties of disperse systems at low shear stresses

Three-dimensional network structures can be built up in disperse systems due to long-range colloidal interactions between the dispersed particles. The rheological behaviour of such coagulation structures has been studied by means of creep and recovery experiments at low shear stresses, i.e. by measuring the shear strain as a function of time under constant stress and after removal of stress. Measurements of this type give insight into the elastic and viscous deformations and the retardation times necessary to reach equilibrium or steady-state conditions.Results obtained with dispersions of pigments in polymer solutions and with monodisperse polymer latexes indicate the existence of an equilibrium state at low shear stresses with a predominant elastic deformation and a high viscosity suggesting that the disperse systems investigated do not behave exactly as rigid gels but apparently exhibit a dynamic equilibrium of structural break-down and formation under applied stress. This behaviour is approximately described by a 4-parameter-model with an instantaneous and a steady-state compliance, one retardation time, and a viscosity.At higher shear stresses thixotropic structural break-down occurs resulting in a transition from the rheological behaviour described here to a liquid-like state with a comparatively low viscosity. In this stress range the viscoelastic properties become strongly time-dependent.These measurements give evidence of the presence of two types of deformation: an instantaneous, purely elastic deformation attributable to the unperturbed coagulation structure and the creep-recovery behaviour of an elastic liquid apparently related to the breaking and re-forming of bonds.     

Determination of elongational viscosity of polymer melts by RME and Rheotens experiments

Several linear (LLDPE, HDPE, PS) and long-chain-branched (LDPE, PP) polymer melts were investigated by an elongational rheometer (RME Rheometrics) and by Rheotens (Göttfert). The Molecular Stress Function (MSF) theory is briefly reviewed and used to extrapolate the steady-state elongational viscosity. To evaluate Rheotens experiments, a new process model is introduced which assumes that the elongational viscosity in the Rheotens test is a function of the draw ratio only. The apparent elongational viscosities extracted from Rheotens curves are found to lie in between the steady-state elongational viscosity and three times the shear viscosity.     

Estimates of apparent elongational viscosity using the fibre spinning and “pure” methods

A comparison is made between elongational properties predicted by the FENE-P dumbbell rheological equation of state for fibre spinning and true values obtained from pure elongation. True values are found by using a constant elongation rate in the model and calculating the steady state values of the stresses. Two new averaging procedures are suggested for extracting elongational properties from fibre spinning experiments. It is suggested that a variety of flow conditions be used and care be taken when determining these properties. The rheological model is found to predict adequately shear and elongational flow properties of the polyacrylamide-type of Boger or ideal elastic fluid.     

Influence of molecular structure on rheological properties of polyethylenes

Elastic properties of melts of a long-chain branched low density polyethylene (LDPE) with a broad molecular mass distribution and a short-chain branched linear low-density polyethylene (LLDPE) with a more narrow molecular mass distribution were investigated by creep recovery measurements in shear. The results obtained by means of a magnetic bearing torsional creep apparatus in the linear-viscoelastic region, showed that the steady state recoverable compliance of the LLDPE is greater by a factor of two than that of the LDPE. In the short-time region up to 1000 s, however, the time-dependent recoverable compliance of the LDPE is higher than that of the LLDPE. The retardation times for the LLDPE are considerably longer than for the LDPE. For the LDPE the temperature dependence of the entanglement transition is consistent with that of the terminal zone of the creep compliance. The activation energy of 58 kJ/mole lies in the typical range for long-chain branched polyethylenes. In the case of the LLDPE the creep compliances can be shifted to give a mastercurve with an activation energy of 34 kJ/mole, whereas the recoverable compliances do not follow the time-temperature superposition principle. The molecular characterization using TREF showed that the LLDPE has a bimodal branching structure. In addition to a short-chain branched component, a low percentage of a linear constituent with high molecular mass was found. It is postulated that this linear component forms a dispersed phase in the matrix of the short-chain branched constituent. The resulting interfacial tension could be the reason for the long retardation times, the high steady state recoverable compliance and the fact that the time-temperature superposition principle is not fulfilled in the case of the LLDPE investigated. Received: 1 July 1997 Accepted: 12 November 1997     

On the elastic properties of model suspensions as investigated by creep recovery measurements in shear

 The elastic properties of model suspensions with spherical monodisperse hydrophilic glass spheres that were dispersed in a Newtonian liquid were determined in creep and creep recovery measurements in shear with a magnetic bearing torsional creep rheometer. The creep and creep recovery measurements were performed depending on the applied level of shear stresses ranging from 0.19 Pa to 200 Pa. Since the recoverable creep compliances of the chosen suspending medium (i.e. a low molecular weight polyisobutylene) were far below the lower limit of the resolution of the creep rheometer it can be considered to behave as purely viscous. By applying a large shear stress in the creep tests the investigated suspensions with a volume fraction of Φ _t =0.35 behave as Newtonian liquids, too. For these suspensions no significant recoverable creep compliances could be detected, as well. In contrast to the Newtonian state of suspensions at high shear stresses, where a shear induced ordering of the particles can be expected, a non-Newtonian behaviour arises by applying a very low shear stress in the creep test. In this state large recoverable creep compliances were detected for the suspensions. The magnitude of the recoverable creep compliances of the suspensions exceeded the largest creep compliances of polymer melts that are reported in the literature by more than two decades. From the results obtained by creep recovery measurements with a magnetic bearing torsional creep rheometer it can clearly be concluded that the particle structure present in the chosen model suspension gives rise to a pronounced elasticity. Received: 21 November 2000 Accepted: 12 July 2001     

Influence of molecular parameters on the stress dependence of viscous and elastic properties of polypropylene melts in shear

The stress dependencies of the steady-state viscosity η and, particularly, that of the steady-state elastic compliance J _e of various linear isotactic polypropylenes (PP) and one long-chain branched PP are investigated using creep-recovery tests. The creep stresses applied range from 2 to 10,000 Pa. In order to discuss the stress-dependent viscosity η and elastic compliance J _e with respect to the influence of the weight average molar mass M _w and the polydispersity factor M _w/M _n the PP are characterized by SEC–MALLS. For the linear PP, linear steady-state elastic compliances J_e⁰J_{\rm e}^0 in the range of 10^− 5–10^− 3 Pa^− 1 are obtained depending on the molar mass distribution. J_e⁰J_{\rm e}^0 of the LCB-PP is distinctly higher and comes to lie at around 10^− 2 Pa^− 1. J_e⁰J_{\rm e}^0 is found to be independent of M _w but strongly dependent on polydispersity. η and J _e decrease with increasing stress. For the linear PP, J _e as a function of the stress τ is temperature independent. The higher M _w/M _n the stronger is the shear thinning of η and the more pronounced is the stress dependence of J _e. For the LCB-PP, the strongest stress dependence of η and J _e is observed. Furthermore, for all PP J _e reacts more sensitively to an increasing stress than η. A qualitative explanation for the stronger stress dependence of J _e compared to η is given by analyzing the contribution of long relaxation times to the viscosity and elasticity.     

Comparison of the elongational behavior of various polyolefins in uniaxial and equibiaxial flows

For processing operations with a pronounced elongational component, it was found that the uniformity of extruded items is improved by the presence of strain hardening usually measured in uniaxial elongation. Many processing operations such as foaming, film blowing, and blow molding are dominated by biaxial deformations, however, and therefore, the question arises how strain hardening in uniaxial and biaxial deformation compares. Besides a linear and long-chain branched PP, one classical LDPE, an HDPE pipe extrusion grade with a bimodal MMD, and a LCB-mPE were also characterized. For the measurements in uniaxial elongation the Münstedt tensile rheometer (MTR) and the ARES-EVF were used, while the lubricated flow method was applied for equibiaxial deformation. It was found that the strain hardening in uniaxial elongation is more pronounced. The dependence of strain hardening on strain rate is qualitatively the same in both modes. In the range of strain rates, the chosen long-chain branched LDPE and PP exhibit a strain hardening, which is approximately independent of the elongational rates applied, whereas for the HDPE it becomes smaller with increasing rate.

The BKZ as an alternative to the Wagner model for fitting shear and elongational flow data of an LDPE melt

For the low density polyethylene Melt I, which is the melt for which the most complete set of shear and elongational data exists, the semi-empirical single integral Wagner model gives an excellent data-fit, but suffers the drawback of having no entropic constitutive equation, that is a relationship between strain history and elastic free energy from which viscous heating and cohesive failure can be predicted. We show here that the BKZ model, which does possess an entropic constitutive equation, gives as good a fit as does the Wagner model to both the shear and elongational data.     

Deformation and orientation during shear and elongation of a polycarbonate/carbon nanotubes composite in the melt

In this study, we focused on the elongational rheology and the morphology of an electrically conductive polycarbonate/multiwalled carbon nanotubes (2 wt%) composite in the melt. In shear and melt elongation, the influence of the carbon nanotubes was large when the externally applied stress was small. Consequently, the elastic interactions resulting from the carbon nanotubes dominated in the low frequency range of the shear oscillations. The elongational viscosity of the composite was only moderately influenced by the addition of 2 wt% carbon nanotubes. Transmission electron microscopy investigations of the stretched composite showed that isolated carbon nanotubes were oriented in elongation. In recovery after melt elongation, the recovered stretch of the composite was much smaller than the recovered stretch of pure polycarbonate. This effect is caused by the carbon nanotubes network, which prohibited large extensions of the macromolecules and led to a yield stress of the composite.     

Rheological properties of long glass fiber filled polypropylene

Long glass fiber-filled polypropylene (PP) composites are produced by pultrusion, and the extrudate is cut at different lengths producing composites containing long fibers of controlled length. The rheological properties of such composites in the molten state have been studied using different rheometers. A capillary rheometer has been constructed and mounted on a molding-injection machine. The shear viscosity of filled PP determined from the capillary rheometer, after corrections for entrance effects, was found to be very close to that of unfilled PP. However, large excess pressure losses at the capillary entrance were observed and these data have been used to obtain an apparent elongational viscosity. The apparent elongational viscosity was shown to be considerably larger than the shear viscosity for PP and filled PP, and it increased markedly with fiber length and fiber content. Rotational rheometers with a parallel-plate geometry were used to investigate the viscoelastic properties of these composites and their behavior was found to be non-linear, exhibiting a yield stress. A model is proposed to describe the shear viscosity from a solid-like behavior at low stresses to fluid-like behavior at high shear stresses taking into account fiber content and orientation. A modified model, proposed for elongational flow, describes relatively well the apparent elongational data.     

The prediction of time-dependent non-linear stresses in viscoelastic materials: II. Prediction of shear and uniaxial elongation behaviour

Stress predictions have been made for two materials using the new strain measure developed in Part I. For the startup of steady-shear flow, the predictions show increasing overshoot of shear and normal stresses at increasing shear rates, and both qualitatively and quantitatively there is good agreement with the experimental results for a polymer solution and a melt. The information contained in Part I on the strain measure is found to be insufficient for making exact predictions for flows other than shear flows, but it is shown here that uniaxial elongational flow is sufficiently similar to shear flow for predictions to be made with only a low degree of inaccuracy. Data on the elongational behaviour of the melt are available from the literature and the predictions made here are found to be in satisfactory agreement with the reported behaviour. All of the predictions require as input information only the linear viscoelastic behaviour of the material.     

Elongational-flow predictions of the Leonov constitutive equation

The basic thermodynamic ideas from rubber-elasticity theory which Leonov employed to derive his constitutive model are herein summarized. Predictions of the single-mode version are presented for homogeneous elongational flows including stress growth following start-up of steady flow, stress decay following sudden stretching and following cessation of steady flow, elastic recovery following cessation of steady flow, energy storage in steady-state flow, and the velocity profile in constantforce spinning. Using parameters of the multiple-mode version which fit the linearviscoelastic data, the Leonov-model predictions of elongational stress growth during, and elastic recovery following, steady elongation are calculated numerically and compared to the experimental results for Melt I and to the Wagner model. It is found that the Leonov model, as originally formulated, agrees qualitatively with the data, but not quantitatively; the Wagner model gives quantitative agreement, but requires much nonlinear data with which to fit model parameters. Quantitative agreement can be obtained with the Leonov model, if the nonequilibrium potential which relates recoverable strain to strain rate is adjusted empirically. This can most simply be done by making each relaxation time dependent upon the recoverable strain. The Leonov model, unlike the Wagner model, is derived from an entropic constitutive equation, which is advantageous for calculating stored elastic energy or viscous dissipation. The Leonov model also has an appealingly simple differential form, similar to the upper-convected Maxwell model, which, in numerical calculations, may be an important advantage over the integral Wagner model.     

Rheological behaviour of nano-composites based on polyamide 6 under shear and elongational flow at high strain rates

In this work, the rheological behaviour of high molecular mass polyamide 6 (PA6)/organo-montmorillonite nano-composites, obtained via melt blending, was investigated under shear and extensional flow. Capillary rheometry was used for the measurement of high shear rate steady state shear viscosity and die entrance pressure losses; further, by the application of a converging flow method (Cogswell model) to these experimental results, elongational viscosity data were indirectly calculated. The extensional behaviour was directly investigated by means of melt spinning experiments, and data of apparent elongational viscosity were determined. The results evidenced that the presence of the organo-clay in filled PA6 melts modifies the rheological behaviour of the material, with respect to the unfilled polymer, in dependence on the type of flow experienced by the fluid. In shear flow, the nano-composites showed a slightly lower viscosity than neat PA6, whereas in elongation, they appeared much more viscous, in dependence on the organo-clay content.     

Modelling elongational and shear rheology of two LDPE melts

Experimental data of two low-density polyethylene (LDPE) melts at 200°C for both shear flow (transient and steady shear viscosity as well as transient and steady first normal stress coefficient) and elongational flow (transient and steady-state elongational viscosity) as published by Pivokonsky et al. (J Non-Newtonian Fluid Mech 135:58–67, 2006) were analysed using the molecular stress function model for broadly distributed, randomly branched molecular structures. For quantitative modelling of melt rheology in both types of flow and in a very wide range of deformation rates, only three nonlinear viscoelastic material parameters are needed: Whilst the rotational parameter, a ₂, and the structural parameter, β, are found to be equal for the two melts considered, the melts differ in the parameter describing maximum stretch of the polymer chains.     

Rheotens-mastercurves and elongational viscosity of polymer melts

In a Rheotens experiment, the tensile force needed for elongation of an extruded filament is measured as a function of the draw ratio. For thermo-rheologically simple polymer melts, the existence of Rheotens-mastercurves was proved by Wagner, Schulze, and Göttfert (1995). Rheotens-mastercurves are invariant with respect to changes in melt temperature and changes in the average molar mass. By use of purely viscous models, we convert Rheotens-mastercurves of a branched and a linear polyethylene melt to elongational viscosity as a function of strain rate. The resulting elongational viscosity from constant force extension experiments is found to be in general agreement with what is expected as steady-state viscosity of polyethylene melts measured in either constant strain-rate or constant stress mode.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     

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.     

Elongational behaviour of a low density polyethylene melt

Summary In addition to earlier findings ofMeißner on a low density polyethylene that in the linear range of deformation the time-dependent elongational viscosity is three times the shear viscosity the validity of the relationship could be demonstrated where and describe the compliances in elongation and shear, respectively. In the nonlinear rangeJ(t) was found to increase with stress whereasD(t) decreases. The nonlinear viscosity-time behaviour is different in shear and elongation, too. The shear viscosity obtained by relating the stress to the rate of viscous strain decreases with shear from the zero shear viscosity to its steady-state value. The elongational viscosity goes up with time from 3 ₀ to a higher steady-state value.The temperature dependence which was determined by measuring the steady-state elongational viscosities at different constant stresses as a function of temperature and by shifting the tensile creep compliancesD(t) measured at constant stress with respect to time, was found to be exactly the same as in shear. This result could indirectly be verified by some constant stretching rate tests. It was shown experimentally that the recoverable strain in the steady-state is independent of temperature if measured at constant stress.

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Zusammenfassung In Ergänzung früherer Ergebnisse vonMeißner an einem Polyäthylen niedriger Dichte, die im linearen Bereich der Verformung für die zeitabhängige Dehnviskosität das Dreifache der Scherviskosität ergaben, konnte die Gültigkeit der Beziehung gezeigt werden. und sind die Nachgiebigkeiten in Dehnung und Scherung. Im nichtlinearen Bereich steigtJ(t) mit zunehmender Spannung an, währendD(t) abfällt. Die Zeitabhängigkeit der Viskosität, definiert als der Quotient aus Spannung und Geschwindigkeit des viskosen Deformationsanteils, ist in Scherung und Dehnung ebenfalls unterschiedlich. Die Scherviskosität fällt von dem Wert der Nullviskosität ₀ mit wachsender Scherung auf einen stationären Wert ab, die Dehnviskosität dagegen steigt von 3 ₀ auf einen höheren stationären Wert an.Die Temperaturabhängigkeit wurde aus Messungen des stationären Wertes der Dehnviskosität bei konstantgehaltener Zugspannung und aus einer Verschiebung der bei unterschiedlichen Temperaturen, aber konstanten Spannungen gemessenen Nachgiebigkeiten in bezug auf die Zeit bestimmt. Sie ist dieselbe wie in Scherung. Dieses Ergebnis konnte indirekt durch Messungen mit konstanter Dehngeschwindigkeit bestätigt werden. Die reversible Dehnung im stationären Zustand wurde bei konstanter Zugspannung als von der Temperatur unabhängig gefunden.

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With 17 figures