The MSF model: relation of nonlinear parameters to molecular structure of long-chain branched polymer melts

The elongational viscosity data of model PS combs (Hepperle J, Einfluss der Molekularen Struktur auf Rheologische Eigenschaften von Polystyrol- und Polycarbonatschmelzen. Doctoral Thesis, University Erlangen-Nürnberg, 2003) are reconsidered by including the interchain pressure term of Marrucci and Ianniruberto [Macromolecules 37:3934–3942, 2004] in the Molecular Stress Function model [Wagner et al., J Rheol 47(3):779–793, 2003, Wagner et al., J Rheol 49:1317–1327, 2005d]. Two nonlinear model parameters are needed to describe elongational flow, β and . The parameterβ determines the slope of the elongational viscosity after the inception of strain hardening. It is directly related to the molecular structure of the polymer and represents the ratio of the molar mass of the (branched) polymer to the molar mass of the backbone alone. β follows from the hypothesis of Wagner et al. [J Rheol 47(3):779–793, 2003] that side chains are compressed onto the backbone. We consider also the case that side chains are oriented by deformation, but not stretched, and found little difference in the model predictions. The parameter represents the maximum strain energy stored in the polymeric system and determines the steady-state value of the viscosity in extensional flows. The relation of this energy parameter to the molecular structure is discussed. Good correlations between the energy parameter and different coil contraction ratios, as determined either experimentally or calculated theoretically by considering the topology of the macromolecule, are found. The smaller the relative size of the polymer coil, the larger is the energy parameter and the more strain energy can be stored in the polymeric system. Presented at the 3rd Annual European Rheology Conference, AERC2006, Crete, Greece.     

Investigation of failure during elongational flow of polymer melts

A basic study of the mechanisms of necking and ductile failure of polymer melts in uniaxial elongational flow has been carried out. A linear stability analysis was carried out using a White—Metzner convected Maxwell model with a deformation-rate-dependent relaxation time, which varies according to τ = τ_o/(1 + aτ_o[2trd²]^{$\text{1}\text{2}$}). It was shown that filament stability and elongation to break depend upon τ_oE, where E is the elongation rate, and a. At fixed τ_oE, filament stability decreases with increasing a. At small a, stability increases with increasing τ_oE while for a > $\text{1}\text{√3}$, stability decreases with increasing τ_oE. For a material with small a, ductile failure can occur for small τ_oE, but cohesive fracture should be the cause of failure at larger τ_oE. For a material with large a, however, ductile failure always dominates the failure mode. These results are used to interpret failure in elongational flow of low density and high density polyethylene and polypropylene melts and describe how the latter two melts exhibit ductile failure.     

Exponential shear flow of branched polymer melts

  The behavior of a low-density polyethylene melt in exponential shear strain histories is examined and compared to its behavior in constant rate planar elongation. A new set of shear stress and first normal stress difference data in exponential shear are presented and used in several different material functions that have been previously proposed. Viscosities composed of principal stress differences for the two flows showed no correspondence suggesting that, contrary to previous assertions, exponential shear and constant rate planar elongation flows are fundamentally different. It is further suggested that the presence of vorticity makes exponential shear a weak, rather than strong, flow. Received: 5 March 1999/Accepted: 1 September 1999     

A hierarchical algorithm for predicting the linear viscoelastic properties of polymer melts with long-chain branching

The hierarchical model proposed earlier [Larson in Macromolecules 34:4556–4571, 2001] is herein modified by inclusion of early time fluctuations and other refinements drawn from the theories of Milner and McLeish for more quantitative prediction. The hierarchical model predictions are then compared with experimental linear viscoelastic data of well-defined long chain branched 1,4-polybutadienes and 1,4-polyisoprenes using a single set of parameter values for each polymer, which are obtained from experimental data for monodisperse linear and star polymers. For a wide range of monodisperse branched polymer melts, the predictions of the hierarchical model for monodisperse melts are very similar to those of the Milner–McLeish theories, and agree well with experimental data for many, but not all, of the branched polymer samples. Since the modified hierarchical model accounts for arbitrary polydispersity in molecular weight and branching distributions, which is not accounted for in the Milner–McLeish theories, the hierarchical algorithm is a promising one for predicting the relaxation of general mixtures of branched polymers.     

A new elongational rheometer for polymer melts and other highly viscoelastic liquids

In polymer melt elongational rheometry only by the rotary clamp technique large elongations can be obtained homogeneously. However, as described in this paper, there still remain disadvantages that led to the development of a new rheometer with the following main features: The dimensions of the required sample are small (60 × 7 × 2 nun³), the sample is supported by a cushion of inert gas and, after having reached the test temperature of up to well above 300°C, it can be extended by a new type of clamps that make use of metal conveyor belts. The resulting tensile force is measured with a resolution of better than 100 mgf (0.001 N). The strain rate range is 0.001-1 s^–1, and the maximum Hencky strain is 7, corresponding to a maximum stretch ratio of 1100. Within the sample, the temperature variation in time and space is less than 0.1°C. For the evaluation and documentation of the test performance, a video camera records the top and side views of the sample that carries a marking powder to permit the evaluation of the true strain rate. The operation of the instrument is easy, and so is the sample preparation, but care must be taken concerning the necessary isotropy and internal homogeneity. Examples of test results are given for several polymer melts at various temperatures: (1) Polystyrene up to a total Hencky strain larger than 7 at 170°C, (2) several types of polyethylene (LDPE, LLDPE, HDPE) at 150°C, (3) poly(amide) at 250°C, and (4) poly(ethersulfone) at 350°C. The wide applicability of the new rheometer is demonstrated by adding results obtained from samples of bread dough. The surface tension has no influence on the results if an error of 3% can be tolerated. From the results it follows that by means of the newly developed rheometer many problems in polymer melt elongation have been solved.Dedicated to Professor Dr. Hermann Janeschitz-Kriegl on the occasion of his 70th birthday.Extended version of a paper presented at the XIth International Congress on Rheology, Brussels, Belgium, August 17–21, 1992.     

Stress and neutron scattering measurements on linear polymer melts undergoing steady elongational flow

We use small-angle neutron scattering to measure the molecular stretching in polystyrene melts undergoing steady elongational flow at large stretch rates. The radius of gyration of the central segment of a partly deuterated polystyrene molecule is, in the stretching direction, increasing with the steady stretch rate to a power of about 0.25. This value is about half of the exponent observed for the increase in stress value σ, in agreement with Gaussian behavior. Thus, finite chain extensibility does not seem to play an important role in the strongly non-linear extensional stress behavior exhibited by the linear polystyrene melt.     

A non-affine network model for polymer melts

In this paper, a network model of polymer melts is proposed in which network junction points move non-affinely. In this non-affine motion, junction points follow particle paths as seen by an observer rotating at the fluid element's net rigid-rotation rate. The speed at which junction points move is reduced as the network segments near their maximum extensions. In order to maintain a frame invariant model, it is necessary that the vorticity be decomposed into two portions, such that, = _R + _D . The deformational vorticity, _D , arises from shear deformation and is frame invariant while the rigid vorticity, _R , is frame dependent. A constitutive equation based on this finitely extensible network strand (FENS) motion is developed. The model illustrates how rotations that cause changes in the relative orientation of a fluid element with its surroundings can be incorporated into a constitutive equation using the deformational vorticity. The FENS model predicts a shear-thinning viscosity, and the Trouton viscosity predicted by the model is finite for all elongation rates. Finally, stochastic simulation results are presented to justify a mathematical approximation used in deriving the constitutive equation.     

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.     

Unsteady flow of polymer melts: Polypropylene

Summary The unsteady flow effect has been studied experimentally in cylindrical capillaries for polypropylene melts with melt indices differing over an approximately 30-fold range. The entrance losses were negligibly small. The flow curves obtained on capillaries of different diameters, coincided, indicating the absence of any considerable near-wall slippage; hence the attainment of unsteady flow is not necessarily due to or accompanied by wall slippage.Two critical regimes can be distinguished distinctly in the flow of polypropylene melts, the first corresponding to the appearance of mattness on the extrudate surface, and the second to the appearance of defects such as a regular spiral with a constant longitudinal pitch. No unsteady flow of the melt fracture type was observed.The shear stresses in the first critical flow regime increase by 40 per cent when the temperature is raised from 180 to 240 °C. Within the same temperature range the stresses corresponding to attainment of the second critical flow regime change by 25 per cent.The critical flow parameters of polypropylene melts grow with increasing capillary length-to-diameter ratio, this effect not being damped even with big capillary lengths.The elastic deformations corrrsponding to attainment of the first critical flow regime of polypropylene melts_e2.7, while that corresponding to the second critical regime _e 3.3 with considerably changed critical stress values.

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Zusammenfassung Der Effekt des nicht-stationären Fließens wurde experimentell in zylindrischen Kapillaren für Polypropylen-Schmelzen mit Schmelz-Indizes zwischen 1 und 30 untersucht. Die Eintrittsverluste waren vernachlässigbar klein. Die Fließkurven, die bei Kapillaren verschiedenen Durchmessers ermittelt wurden, stimmten überein und zeigten das Fehlen irgendwelcher Gleitung in der Nähe der Wand. Demnach ist das Entstehen eines nicht-stationären Fließens nicht notwendigerweise abhängig bzw. begleitet von einer Wandgleitung.Zwei kritische Bereiche können eindeutig beim Fließen von Polypropylen-Schmelzen unterschieden werden: der erste im Zusammenhang mit dem Auftreten einer matten Extrudat-Oberfläche und der zweite mit dem Auftreten von Fehlern wie einer regelmäßigen Spirale mit konstanter Steigung. Ein nicht-stationäres Fließen vom Schmelzbruchtyp wurde nicht beobachtet.Die Schubspannung in dem ersten kritischen Fließbereich wächst bei einem Temperaturanstieg von 180 auf 240 °C um 40%. Im gleichen Temperaturbereich wachsen die Spannungen bei Erreichen des zweiten kritischen Fließgebietes um 25%.Die kritischen Fließparameter von Polypropylen-Schmelzen wachsen mit steigendem Verhältnis Kapillarlänge zu Durchmesser, wobei dieser Effekt auch durch große Kapillarlängen nicht gedämpft wird. Die elastischen Deformationen, die bei Erreichen des ersten kritischen Fließgebietes von Polypropylen-Schmelzen auftreten, betragen _e 2,7, während für das zweite kritische Gebiet bei deutlich geänderten kritischen Spannungswerten sich Deformationen von _e 3,3 ergeben.

     

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.     

A new elongational rheometer for polymer solutions

Design and operation of a new elongational rheometer for low elastic polymer solutions are described. The free jet elongational rheometer is easy to operate and for suitable operating conditions a transient elongational flow with an approximately constant rate of strain can be realized. In any case, convenient comparative parameters can be obtained. The method of rheological curve fitting leads to a deformation dependent ralaxation time parameter of a modified upper convected Jeffreys-law.     

A model for interpreting die swell of polymer melts

Summary We propose here a new model to interpret the most peculiar characteristics of die swelling of polymer melts.The model, which applies to short capillaries, is based on the observations that the deformation undergone by the melt entering the capillary from the reservoir is essentially elastic and that the deformation within the capillary is essentially viscous.Under these assumptions we can derive an equation for the deformation of the polymer emerging from the capillary, which is a measure of swelling.In order to check the validity of this equation swelling experiments were performed on high density polyethylene by using a technique of annealing the strands in silicon oil after extrusion.Quite satisfactory agreement between theory and experiments was found, provided that the characteristic relaxation time,, was properly evaluated. In fact it turned out that is of the order of magnitude of the time at which the shear stress fully relaxes in an experiment of stress relaxation after steady state shear flow.

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Zusammenfassung Es wird ein neues Modell zur Erklärung der wesentlichsten Züge der Strahlaufweitung bei Polymerschmelzen vorgeschlagen. Dieses Modell, das auf kurze Kapillaren beschränkt ist, basiert auf der Beobachtung, daß die von der Schmelze beim Einströmen aus dem Reservoir in die Kapillare ausgeführte Deformation im wesentlichen elastisch, die Deformation beim Durchgang durch die Kapillare dagegen im wesentlichen viskos ist.Unter diesen Voraussetzungen wird eine Gleichung für die Deformation des aus der Kapillare austretenden Polymers angegeben, welche ein Maß für die Aufweitung liefert.Zur Prüfung dieser Gleichung werden Strahlaufweitungsexperimente mit hochdichtem Polyäthylen ausgeführt, wobei das Extrudat in Siliconöl getempert wird.Zwischen Theorie und Experimenten wird eine recht befriedigende Übereinstimmung gefunden, vorausgesetzt daß die charakteristische Relaxationszeit in angepaßter Weise bestimmt wird. Es stellt sich heraus, daß von der Größenordnung derjenigen Zeit ist, bei der die Schubspannung nach voraufgegangener stationärer Scherströmung vollständig relaxiert ist.

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With 7 figures and 3 tables     

Linear rheology of diluted linear, star and model long chain branched polymer melts

We present experiments and theory on the diluted melt dynamics of monodisperse entangled polymers of linear, star and H-shaped architecture. Frequency-dependent rheological data on a series of progressively diluted linear, star and H-polymers are in good agreement with a refined tube-model theory that, for H-polymers, combines star polymer melt behaviour at high frequency, with linear polymer reptation behaviour at low frequencies. Taking into account the effect of dilution via some simple scaling relations, mild polydispersity and by incorporating the high frequency Rouse modes, we are able to model quantitatively the entire frequency range. This work suggests a novel rheological route to analysing long chain branching in polymer melts. Received: 6 April 2000/Accepted: 21 December 2000     

A network model with free-strand dynamics for polymer melts

 A network model for polymer melts is presented in which disentangled strands relax under flow conditions and may rejoin the network before complete relaxation. For simplicity, we study Gaussian strands that move affinely when incorporated in the network. Network strands are created and lost according to a time constant λ. Free strands have their dynamics given by the Bird-DeAguiar model as a crude representation of reptation and the hindered rotation experienced by polymer strands in melts. The model yields a shear-thinning viscosity with overshoot in the start-up viscosity η⁺ (t). The double-step strain results compare well with available experimental data. Received: 10 July 2000 Accepted: 10 July 2001     

Relaxational interactions and viscoelasticity of polymer melts. Part I: model development

Rheological equations of state for the concentrated solutions and melts of high polymers are derived by applying a structural approach. The dynamics of a macromolecule are considered on the basis of the fundamental model of the polymer chain, e.g., the bead-spring model. The drag forces describing correlations of motion macromolecules are determined by means of the relaxation equations. The oscillatory shearing flow of the melts is studied on the basis of the equations derived. Expressions for the dynamic modulus and relaxation times are determined. As can be judged from the form of the dependence of the dynamic modulus on frequency, the relaxation time distribution is the same as in real materials. The relaxation spectrum of high polymers has a terminal zone with abnormally long relaxation times.     

Numerical study of the rheology of rigid fillers suspended in long-chain branched polymer under planar extensional flow

We report a detailed numerical study of the rheology of two-dimensional rigid fillers suspended in branched polymer melt under planar extensional flow. The polymer melt is modelled using the pom-pom constitutive equation. The numerical method uses a finite element solution of the flow in a unit cell within the self-replicating lattice for planar extensional flow identified by Kraynik and Reinelt [Int. J. Multiphase flow 18 (1992) 1045]. This is implemented using a quotient space representation that maps all points in space onto points within the unit cell. We show that the Kraynik and Reinelt cell allows simulations of suspensions under planar extensional flow to be conducted to large strains in a truly periodic cell. The influence of both the pom-pom parameters and the particle area fraction on the rheology of the suspension are investigated. We find a reduction in the degree of extension-rate thickening with the increase of both particles concentration and Weissenberg numbers in agreement with published experimental and numerical findings on other viscoelastic models. This reduction is found to be due to flow disturbance created by the particles which disrupts the alignment of backbone tube segments with the extensional axis.     

Experiments on elongational flow of dilute polymer solutions Part I: Jet reaction and excess pressure drop for the flow through small apertures

Experiments have been made with dilute polymer solutions on the reaction of jets issuing from small orifices and the excess pressure drop for orifice and capillary flows.Under the flow conditions with vortices occurring upstream of the aperture, the jet reaction is nearly zero below some mean velocity for PEO solutions and similarly zero below some generalized Reynolds number for Separan solutions. The normalized jet reactions, when they possess positive values, are correlated with the generalized Reynolds number irrespective of the aperture diameters for both kinds of solution.In most cases, the pressure is higher than in the corresponding water flow, but for some flows with no vortex it is lower. For the vortex flow of PEO solutions the normalized excess pressure drop is inversely proportional to the Reynolds number for both orifices and capillaries, while for Separan solutions this quantity is not correlated with the generalized Reynolds number for orifice flow but is correlated with it for capillary flow.     

Testing of a constitutive equation for entangled networks by elongational and shear data of polymer melts

Summary An entangled network such as a polymer melt or a concentrated solution is here described by a set of two simultaneous equations. One of them is a balance of entanglements, the other gives the stress in the classical form of aMaxwell equation.The balance of entanglements contains both an entanglement generation term which depends on the distance from equilibrium and an entanglement destruction term which depends on the stress level. The parameters appearing in theMaxwell and the balance equations are made to depend in a specified way on the existing number of entanglements.The model is here tested by comparison with existing data of steady-state elongational and shear viscosity of polymer melts.With 6 figures