Elongational,shear and volume viscosities of polymer melts

Volume viscosity of polypropylene, polystyrene, and low density polyethylene are described. Shear, elongational, and volume viscosities may be interrelated with the help of scaling equations. They explain the effect on elongational viscosity of strain rates, stresses, and strains.     

Elongational flow opto-rheometry for polymer melts

Polymer melt elongation is one of the most important procedures in polymer processing. To understand its molecular mechanisms, we constructed an elongational flow opto-rheometer (EFOR) in which a high precision birefringence apparatus of reflection-double path type was installed into a Meissner's new elongational rheometer of a gas cushion type (commercialized as RME from Rheometric Scientific) just by mounting a small reflecting mirror at the center of the RME's sample supporting table. The EFOR enabled us to achieve simultaneous measurements of tensile stress (t) and birefringence n(t) as a function of time t under a given constant strain rate within the range of 0.001 to 1.0s^–1. (t) can be monitored upto the maximum Hencky strain (t) of 7 as attained, in principle, with RME, while the measurable range of the phase difference in the birefringence was 0 to 250 (0 to 79 100 nm for He-Ne laser light) within the accuracy of ±0.1 (±31.6 nm) up to (t) 4. The performance was tested on an anionically polymerized polystyrene (PS) and a low density polyethylene (LDPE). For both polymers (t) first followed the linear viscoelasticity rule in that the elongational viscosity, , is three times the steady shear viscosity, 3 _o(t), at low shear rate , but the _E (t) tended to deviate upward after a certain Hencky strain was attained. The birefringence n(t) was a function of both Hencky strain and strain rate in such a way that the stress-optical law holds with the stress-optical coefficient C(t) = n(t)/(t) being equal to the ones reported from shear flow experiments. Interestingly, however, for PS elongated at low strain rates the C(t) vs (t) relation exhibited a strong nonlinearity as soon as (t) reached steady state. This implies that the tensile stress reaches the steady state but the birefringence continues to increase in the low strain-rate elongation. For the PS melt elongated at high strain rates, on the other hand, C(t) was nearly a constant in the entire range observed. For LDPE with long-chain branchings, (t) exhibited tendency of strain-induced hardening after certain critical strain, but C(t) was nearly a constant in the entire range of (t) observed.     

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     

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.     

The role of instrument compliance in normal force measurements of polymer melts

Schweizer et al. [J Rheol 48(6):1345–1363, 2004] showed nonlinear step shear rate data for a polystyrene melt (M _w=200 kg/mol, M _w/M _n=1.06, T=175°C). For different rheometers, cone angles, and sample sizes, the delayed normal force rise observed therein relative to a compliance-free reference N ₁ (from a thermodynamically consistent reptation model) is shown to depend on rheometer compliance characterized by the instrument stiffness K _A. K _A can be obtained from mapping N ₁ on the measured N _1,meas. or directly from mechanical contact measurement with a mismatch of 20–30%. The ranking of the stiffnesses found is K _A(RMS 800)>K _A(MCR 300)>K _A(ARES LR2). Once K _A is known, N _1,meas.-data can be corrected by solving the ill-posed Volterra equation involved in it. The correction shown for experiments with the 0.15-rad cone angle gives very good results. The characteristic decay time of the normal force after cessation of flow scales linearly with the axial response time t _a calculated from K _A, cone angle, and sample radius. The torque decay time is practically independent of t _a.Extended Version of a paper presented at the 2nd Annual European Rheology Conference in Grenoble, France, April 21–25, 2005.     

Some aspects of linear and nonlinear viscoelastic behaviour of polymer melts in shear

In linear viscoelastic investigations the frequency dependence of the phase shift between stress and strain appears to be very characteristic of the molecular structure of the material. This function is also a good approximation of the slope of the double logarithmic plot of the absolute value of the shear modulusG _d vs. the angular frequency. The product (G _d /) sin 2 comes very close to the relaxation spectrumH(), with = 1/, in all physical states of the material.The experimentally observed separability of time and strain effects in nonlinear viscoelasticity of highly viscous isotropic polymer fluids imposes restraints to the form of the constitutive equation. A single integral superposition equation of the Boltzmann type containing the product of a time function and a nonlinear strain function gives good results in describing experimental data in shear as well as in elongation. The molecular structure affects both functions in a different way. A universal definition of the nonlinear tensorial strain measure has not yet been developed. There are some indications that a definition on the basis of the principal stretch ratios may be fruitful.Invited paper, presented at the First Conference of European Rheologists at Graz (Austria), April 14–16, 1982.     

Elongational rheology of polyethylene melts — temporary network constitutive laws

The uniaxial elongational properties of various polyethylenes have been evaluated using an elongational rheometer and a melt-strength apparatus. It is possible to derive the data obtained in elongation from the distribution of relaxation times obtained from oscillatory shearing measurements (linear viscoelasticity), using a Wagner constitutive equation. The effects of the molecular parameters of the samples have been studied, in particular the effect of polydispersity on the shape of the damping function.     

Towards a rheological classification of flow induced crystallization experiments of polymer melts

Departing from molecular based rheology and rubber theory, four different flow regimes are identified associated to (1) the equilibrium configuration of the chains, (2) orientation of the contour path, (3) stretching of the contour path, and (4) rotational isomerization and a deviation from the Gaussian configuration of the polymer chain under strong stretching conditions. The influence of the ordering of the polymer chains on the enhanced point nucleation, from which spherulites grow, and on fibrous nucleation, from which the shish-kebab structure develops, is discussed in terms of kinetic and thermodynamic processes. The transitions between the different flow regimes, and the associated physical processes governing the flow induced crystallization process, are defined by Deborah numbers based on the reptation and stretching time of the chain, respectively, as well as a critical chain stretch. An evaluation of flow induced crystallization experiments reported in the literature performed in shear, uniaxial and planar elongational flows quantitatively illustrates that the transition from an enhanced nucleation rate of spherulites towards the development of the shish-kebab structure correlates with the transition from the orientation of the chain segments to the rotational isomerization of the high molecular weight chains in the melt. For one particular case this correlation is quantified by coupling the wide angle X-ray diffraction and birefringence measurements of the crystallization process to numerical simulations of the chain stretch of the high molecular weight chains using the extended Pom-Pom model in a cross-slot flow.     

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     

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     

Modelization of extensional experiments under constant force using memory-integral constitutive equations and stream-tube analysis

In this paper, we propose a numerical simulation of axisymmetric extensional experiments on a viscoelastic polydimethylsiloxane (PDMS) material, using a falling-weight extensional rheometer. The polymer behaviour is represented by a K-BKZ memory-integral constitutive equation, involving a damping function of the Wagner type. Under the assumption of a homogeneous flow zone in the sample, a numerical model is set up, using the stream-tube method and approximating functions. The governing equations of the problem, associated to a limited number of unknowns, are solved by means of the Levenberg-Marquardt optimization algorithm. The numerical results are found to be consistent with the experimental data and reveal the importance of the non-homogeneous flow zone, in relation to the estimation of the extensional strain rate. The calculations involve the sensitivity of the model on the fluid parameters and those concerning the size of the initial column of fluid. The limited computing (CPU) time of the code is also to be underlined.     

Quasi-linear rheological behaviour of polymer melts: Comparison between mechanical and improved flow birefringence measurements

Summary The latest improvement of the rotor unit (cone- and plate-type) for the measurement of the flow-birefringence of polymer melts is described. As a consequence of this improvement, the influence of parasitic birefringences, as produced in the corners near the windows, is minimized. It is shown that the limitation of the range of available rates of shear, as experienced with previous versions of the apparatus, was due to those parasitic birefringences which predominated at rates of shear where the main birefringence caused an optical path difference of one, two or more whole wavelengths (fringes) and was, as a consequence, virtually zero. This explains why great troubles were experienced in particular with polymers possessing a high back-bone anisotropy. The validity of the linear stress-optical rule up to shear rates, where melt fracture occurs in capillary flow, is well understood in terms of the wriggling motion of chain molecules. Comparison with direct mechanical measurements was very satisfactory.

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Zusammenfassung Eine Beschreibung der jüngsten Verbesserung an der Rotorzelle (Kegel-Platte-Typ) für die Messung der Strömungsdoppelbrechung polymerer Schmelzen wird gegeben. Als Folge dieser Verbesserung wird der Einfluß der parasitären Doppelbrechung, die in den Ecken neben den Fenstern auftritt, minimalisiert. Es wird gezeigt, daß die Begrenzung des Bereiches der verfügbaren Schergeschwindigkeiten, wie sie in früheren Versionen des Apparates gefunden wurde, auf das Vorherrschen der parasitären Doppelbrechungen bei Schergeschwindigkeiten zurückzuführen ist, bei denen die Hauptdoppelbrechung optische Weglängen von einer, zwei oder mehreren ganzen Wellenlängen verursacht und daher effektiv null wird. Dies erklärt, warum große Schwierigkeiten gerade bei solchen Polymeren auftraten, die eine stärkere Kettenanisotropie aufweisen. Die Gültigkeit der linearen spannungsoptischen Regel bis zu Schergeschwindigkeiten, bei denen in der Kapillaren Schmelzbruch auftritt, kann man aufgrund der Ringelbewegung der Makromoleküle gut verstehen. Ein Vergleich mit direkten mechanischen Messungen ergab sehr befriedigende Ergebnisse.

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With 8 figures and 2 tables     

Comparison of the elongational behaviour of a polyethylene melt at constant stress and constant strain rate

Summary Two different apparatuses for measuring the elongational behaviour of polymer melts at constant tensile stress and constant elongational strain rate are described. Measurements on a low density polyethylene were carried out up to stretching ratios of 400. The homogeneity of sample deformation in both test methods was sufficient to reach a steady-state of elongational flow where the tensile stress and the strain rate as functions of time are constant. By unloading the molten rod the recoverable strain can be determined at any state of deformation. The recoverable strain increases with growing deformation and reaches a constant value in the steady-state. The elongational viscosity calculated from the rate of viscous flow agrees with the Trouton viscosity in the case of very small deformations only. With growing deformation the elongational viscosity increases up to a constant value in the steady-state which is greater than the Trouton viscosity by about a factor of six at measured strain rates of 0.03 s^–1 and 0.1 s^–1, respectively. The elongational viscosity and the recoverable strain in the steady-state measured with the two different test methods under the same experimental conditions are in good agreement.

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Zusammenfassung Zwei verschiedene Apparaturen zur Untersuchung des Dehnverhaltens von Polymerschmelzen unter konstanter Zugspannung und konstanter Dehngeschwindigkeit werden beschrieben. An einem Polyäthylen niedriger Dichte wurden Messungen bis zu Verstreckgraden von 400 durchgeführt. Die ausreichend homogene Probenverformung erlaubt in beiden Versuchsführungen das Erreichen eines stationären Dehnfließens mit zeitlich konstanter Zugspannung und Dehngeschwindigkeit. Durch Entlasten des Schmelzestranges ist der reversible Dehnungsanteil für jeden Verformungszustand direkt zu messen. Die reversible Dehnung steigt mit wachsender Dehnverformung an, bis sich im stationären Bereich ein konstanter Wert einstellt. Die aus der Geschwindigkeit des viskosen Dehnfließens berechnete Dehnviskosität stimmt nur für den Grenzfall kleiner Deformationen mit der Trouton-Viskosität überein. Mit wachsender Dehndeformation steigt die Dehnviskosität bis zu einem Gleichgewichtswert an, der bei den gemessenen Dehngeschwindigkeiten von 0,03 s^–1 und 0,1 s^–1 um etwa einen Faktor 6 über dem Wert der Trouton-Viskosität liegt. Die unter gleichen Versuchsbedingungen mit beiden Apparaturen bestimmten Dehnviskositäten und reversiblen Dehnungen im stationären Bereich stimmen überein.

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Parts of this paper were presented at the VII^th Internat. Congress on Rheology, Gothenburg, Sweden.

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With 10 figures and 2 tables     

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.