Equibiaxial extensional flow of polymer melts via lubricated squeezing flow. II. Flow modeling

A model for lubricated squeezing flow of a viscoelastic fluid is developed in order to study the viability of this flow as a rheological technique for generating equibiaxial extensional deformations in polymer melts. In this simple flow model, the melt, described by an upper-convected Maxwell fluid, is squeezed between thin films of a Newtonian fluid. Comparisons of the model predictions for constant strain rate and constant stress flows are made with experimental results presented in the first paper. Predictions from the model are able to describe the effects of lubricant viscosity and experimental configuration and indicate the technique fails for these flows at Hencky strains of approximately one. The cause for this failure is lubricant thinning, which leads to significant errors in both the measured stress difference and the strain. Received: 31 January 2000 Accepted: 31 May 2000     

Fingerprinting the processing behavior of polyethylenes from transient extensional flow and peel experiments in the melt state

The flow curves of linear (linear-low and high density) and branched polyethylenes are known to differ significantly. At increasing shear rates, the linear polymers exhibit a surface melt fracture or sharkskin region that is followed by an unstable oscillating or stick-slip flow regime when a constant piston speed capillary rheometer is used. At even higher shear rates, gross melt fracture appears. Unlike their linear counterparts, branched polyethylenes rarely exhibit sharkskin melt fracture and although gross melt fracture appears at high shear rates there is no discontinuity in their flow curve. The various flow regimes of these two types of polyethylenes are examined by performing experiments in the melt state using a unique extensional rheometer (the SER by Xpansion Instruments) that is capable of performing accurate extensional flow and peel experiments at very high rates not previously realized. The peel strength curves of these linear and branched polyethylenes exhibit all of the distinct flow regimes exhibited in their respective flow curves, thereby providing a fingerprint of their melt flow behavior. Moreover, these extensional flow and peel results in the melt state provide insight into the origins and mechanisms by which these melt flow phenomena may occur with regard to rapid tensile stress growth, melt rupture, and adhesive failure at the polymer wall interface.     

Prediction of extrudate swell in polymer melt extrusion using an Arbitrary Lagrangian Eulerian (ALE) based finite element method

Accurate prediction of extrudate (die) swell in polymer melt extrusion is important as this helps in appropriate die design for profile extrusion applications. Extrudate swell prediction has shown significant difficulties due to two key reasons. The first is the appropriate representation of the constitutive behavior of the polymer melt. The second is regarding the simulation of the free surface, which requires special techniques in the traditionally used Eulerian framework. In this paper we propose a method for simulation of extrudate swell using an Arbitrary Lagrangian Eulerian (ALE) technique based finite element formulation. The ALE technique provides advantages of both Lagrangian and Eulerian frameworks by allowing the computational mesh to move in an arbitrary manner, independent of the material motion. In the present method, a fractional-step ALE technique is employed in which the Lagrangian phase of material motion and convection arising out of mesh motion are decoupled. In the first step, the relevant flow and constitutive equations are solved in Lagrangian framework. The simpler representation of polymer constitutive equations in a Lagrangian framework avoids the difficulties associated with convective terms thereby resulting in a robust numerical formulation besides allowing for natural evolution of the free surface with the flow. In the second step, mesh is moved in ALE mode and the associated convection of the variables due to relative motion of the mesh is performed using a Godunov type scheme. While the mesh is fixed in space in the die region, the nodal points of the mesh on the extrudate free surface are allowed to move normal to flow direction with special rules to facilitate the simulation of swell. A differential exponential Phan Thien Tanner (PTT) model is used to represent the constitutive behavior of the melt. Using this method we simulate extrudate swell in planar and axisymmetric extrusion with abrupt contraction ahead of the die exit. This geometry allows the extrudate to have significant memory for shorter die lengths and acts as a good test for swell predictions. We demonstrate that our predictions of extrudate swell match well with reported experimental and numerical simulations.     

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     

Approximate elongation flow properties utilising the opposed orifice technique – Correction for shear and inertia

Mackay et al. (1995) have presented an approximate technique to determine the elongation viscosity from pressure drop measurements in a simple stagnation flow device. In the present paper we describe experiments using a high viscosity Newtonian oil, aimed at probing some of the assumptions made by Mackay et al. We find that Trouton ratios calculated using the original analysis are well above the value of three expected for Newtonian fluids. Finite element simulations of the flow field show this is due to the net pressure drop having a substantial shear contribution, which should be corrected for before the Trouton ratios are evaluated. Interestingly, most of the shear correction is due to shear on the inside of the orifice near the exit from the central flow region. The shear contribution to the pressure drop occurs for all flow rates, however, at large flow rates there is also an inertial correction to the pressure drop. In this paper we describe an approximate method that corrects for both shear and inertial effects. With these effects recognised and corrected for, the measured Trouton ratios are reduced to around three. Received: 15 December 1997 Accepted: 16 March 1998     

A novel technique for conducting creep experiments in equibiaxial elongation

A recently developed rheological technique known as continuous lubricated squeezing flow (CLSF) is adapted to perform constant stress, or creep, experiments in equibiaxial elongation flows of polymer melts. By modifying the CLSF technique, which was developed for constant strain rate deformations, we demonstrate that the technique can also be used to generate constant stress flows. Measured steady state viscosities are compared to constant rate elongation results for polymer melts having different molecular characteristics. Linear polymers show strain softening and compare well in constant stress and constant strain rate deformations. The branched polymer shows strain hardening and a viscosity that is slightly higher in constant stress for low rates. Limitations of the current version of the CLSF technique for creep flows are also briefly discussed.     

Elongational flow behavior of polymeric fluids according to the Leonov model

The viscoelastic behavior of polymeric systems based upon the Leonov model has been examined for (i) the stress growth at constant strain rate, (ii) the stress growth at constant speed and (iii) the elastic recovery in elongational flow. The model parameters have been determined from the available rheological data obtained either in steady shear flow (shear viscosity and first normal-stress difference as a function of shear rate) or oscillatory flow (storage and loss moduli as a function of frequency in the linear region) or from extensional flow at very small strain rates (time-dependent elongation viscosity in the linear viscoelastic limit). In addition, the effect of the parameter characterizing the strain-hardening of the material during elongation has also been studied. The estimation of this parameter has been based upon the structural characteristics of the polymer chain which include the critical molecular weight and molecular weight of an independent segment. Five different polymer melts have been considered with varying number of modes (maximum four modes). Resulting predictions are in fair agreement with corresponding experimental data in the literature.     

Extensional rheology of concentrated poly(ethylene oxide) solutions

The shear and extensional rheology of three concentrated poly(ethylene oxide) solutions is examined. Shear theology including steady shear viscosity, normal stress difference and linear viscoelastic material functions all collapse onto master curves independent of concentration and temperature. Extensional flow experiments are performed in fiber spinning and opposed nozzles geometries. The concentration dependence of extensional behavior measured using both techniques is presented. The zero-shear viscosity and apparent extensional viscosities measured with both extensional rheometers exhibit a power law dependence with polymer concentration. Strain hardening in the fiber spinning device is found to be of similar magnitude for all test fluids, irrespective of strain rate. The opposed nozzle device measures an apparent extensional viscosity which is one order of magnitude smaller than the value determined with the fiber spinline device. This could be attributed to errors caused by shear, dynamic pressure, and the relatively small strains developed in the opposed nozzle device. This instrument cannot measure local kinematics or stresses, but averages these values over the non-homogenous flow field. These results show that it is not possible to measure the extensional viscosity of non-Newtonian and shear thinning fluids with this device. Fiber spin-line experiments are coupled with a momentum balance and constitutive model to predict stress growth and diameter profiles. A one-mode Giesekus model accurately captures the plateau values of steady and dynamic shear properties, but fails to capture the gradual shear thinning of viscosity. Giesekus model parameters determined from shear rheology are not capable of quantitatively predicting fiber spinline kinematics. However, model parameters fit to a single spinline experiment accurately predict stress growth behavior for different applied spinline tensions.     

Modeling flow induced crystallization in film casting of polypropylene

Data from iPP film casting experiments served as a basis to model the effect of flow on polymer crystallization kinetics. These data describe the temperature, width, velocity and crystallinity distributions along the drawing direction under conditions permitting crystallization along the draw length.In order to model the effect of flow on crystallization kinetics, a modification of a previously defined quiescent kinetic model was adopted. This modification consisted in using a higher melting temperature than in the original quiescent model. The reason for the modification was to account for an increase of crystallization temperature due to entropy decrease of the flowing melt. This entropy decrease was calculated from the molecular orientation on the basis of rubber elasticity theory applied to the entangled and elongated melt. The evolution of molecular orientation (elongation) during the film casting experiments was calculated using a non-linear dumbbell model which considers the relaxation time, obtained from normal stress difference and viscosity functions, to be a function of the deformation rate.The comparison between experimental distributions and model based crystallinity distributions was satisfactory.     

Birefringence measurements on polymer melts in an axisymmetric flow cell

 The stress-optical rule relates birefringence to stress. Consequently, measurement of flow birefringence provides a non-intrusive technique of measuring stresses in complex flows. In this investigation we explore the use of an axisymmetric geometry to create a uniaxial elongational flow in polymer melts. In axisymmetric flows both birefringence and orientation angle change continuously along the path of the propagating light. The cumulative influence of the material's optical properties along the light's integrated path makes determination of local birefringence in the melt impossible. One can nevertheless use birefringence measurements to compare with predictions from computer simulations as a means of evaluating the constitutive equations for the stress. More specifically, in this investigation we compare the light intensity transmitted through the experimental set-up vs entry position, with the theoretically calculated transmitted intensity distribution as a means of comparing experiment and simulation. The main complication in our experiments is the use of a flow cell that necessarily consists of materials of different refractive indices. This introduces refraction and reflection effects that must be modeled before experimental results can be correctly interpreted. We describe how these effects are taken into account and test the accuracy of predictions against experiments. In addition, the high temperatures required to investigate polymer melts mean that a further complication is introduced by thermal stresses present in the flow cell glass. We describe how these thermal-stresses are also incorporated in the simulations. Finally, we present some preliminary results and evaluate the success of the overall method. Received: 2 April 2001 Accepted: 27 August 2001     

Non-isothermal transient flow and molecular orientation during injection mold filling

The properties of injection molded products are directly related to the microstructure which in turn strongly depends on the flow kinematics and thermal history of the polymer melt during the filling process. In this study the mold filling process has been analyzed by using an FEM-code (FIDAP) to solve the equation of continuity, momentum, and energy under transient and non-isothermal conditions. As constitutive relation for a purely viscous fluid, the Bird-Carreau and Arrhenius model was chosen. The phenomenon at the flow front, its flow kinematics, and its significant implication on the microstructure of the part have been investigated in detail. Computed particle tracking showed good agreement with experiments under real processing conditions. Furthermore, a rather simple but effective and useful method for predicting the orientation distribution in an injection molded part was proposed. It was found that the local deformation near the solid wall may be considered as the main source for a typical layer of high orientation on the surface of the part. Received: 1 December 1999 Accepted: 9 August 2000     

The effect of slip in the flow of a branched PP melt: experiments and simulations

In this paper visualisation and direct velocity profile measurement experiments for a branched polypropylene melt in a 10:1 axisymmetric contraction demonstrate the onset of wall slip. Video processing of the flow shows the formation of vortices and their diminution with increasing flow rate. Numerical simulations using a multimode K-BKZ viscoelastic and a purely viscous (Cross) model—both of them incorporating a nonlinear slip law—were used to predict the flow kinematics and dynamics as well as to deduce the slip velocity function by performing fitting to the velocity profiles. It was found that the numerical predictions agree well with the experimental results for the velocity profiles, and vortex formation, growth and reduction. It is suggested that such experiments (visualisation of entrance flow and direct velocity profile measurement) can be useful in evaluating the validity of constitutive equations and slip laws in the flow of polymer melts through processing equipment.     

Stability of plane poiseuille flow of a highly elastic liquid

The stability of fully developed pressure driven plane laminar flow of a Maxwell fluid has been studied using linear hydrodynamic stability theory. Elasticity is destabilizing in the inertial regime, but the flow is found to be stable to infinitesimal disturbances at low Reynolds numbers. This result contradicts previous calculations, which predicted a low Reynolds number flow instability at a critical recoverable shear of order unity. The previous calculations were carried out using less accurate numerical methods; the eigenvalue problem which must be solved is a delicate one, requiring sophisticated umerical techniques in order to avoid the calculation of spurious unstable modes.This work has direct bearing on the question of the mechanism of a low Reynolds number extrusion instability known as “melt fracture”. It is observed that the intensity of melt fracture increases with increasing die length for high density polyethylene, and it is therfore believed by some experimentalists that fully-developed die flow is unstable for this polymer above a critical recoverable shear. The analysis appears to be at variance with this interpretation of the experimental results.     

Microstructure and melt flow behavior of a starch-based polymer

Results on some physical properties and on melt processing of a starch-based polymer under steady-state shearing are presented. A peculiar microstructure involving a strong pseudoplastic behavior at high shear rates as well as yield stress at lower ones is discussed. A model is proposed to explain the characteristic viscoelastic behavior of this material based on hydrophylic and hydrophobic interactions between starch and vinyl-alcohol copolymers.In spite of the highly structured and composite nature of this class of materials, the full body of results reveals that they can be easily processed by means of common manufacturing techniques involving melt pumping and die forming. A comparison with a low density polyethylene (LDPE) grade for film blowing is also shown.     

A Reynolds stress model for turbulent flow of homogeneous polymer solutions

Using a priori analyses of direct numerical simulation (DNS) data, a Reynolds stress model (RSM) is developed to account for the influence of polymer additives on turbulent flow over a wide range of flow conditions. The Finitely Extensible Nonlinear Elastic-Peterlin (FENE-P) rheological constitutive model is utilized to evaluate the polymer contribution to the stress tensor. Thirteen DNS data sets are used to analyze the budgets of elastic stress–velocity gradient correlations as well as Reynolds stress and dissipation transport. Closures are developed in the framework of the RSM model for all the required unknown and non-linear terms. The polymer stresses, velocity profiles, turbulent flow statistics and the percentage of friction drag reduction predicted by the RSM model are in good agreement with present and those obtained from independent DNS data over a wide range of rheological and flow parameters.     

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.     

Prediction of residual flow and thermoviscoelastic stresses in injection molding

A general model for predicting the total residual stresses generated during filling and cooling stages of injection-molded parts has been developed. The model takes into account the phenomena associated with non-isothermal stress relaxation. The main hypothesis in our approach is to use the kinematics of a generalized Newtonian fluid at the end of the filling stage as the initial state for the calculation of residual flow stresses. These stresses are calculated using a single integral rheological model (Wagner model). The calculation of stresses developed during the cooling stage is based on a thermoviscoelastic model with structural relaxation. Illustrative results emphasizing the effect of both the melt temperature and the flow rate during the filling stage are presented.     

Effect of pressure-dependent slip on flow curve multiplicity

Various microstructural pictures for slip at polymer/solid interfaces lead to relations which have a region where multiple values of slip velocity are predicted for the same shear stress. This leads to the expectation of multivalued flow curves, which has been verified in specific cases by numerous researchers. We study the effect of pressure dependence on flow curve multiplicity using a simple multivalued slip relation to model the phenomena of hysteresis and spurt flow in polymer extrusion. A continuation technique is used to trace out the boundaries of the region of flow curve multiplicity as pressure drop and die length to diameter (L/D) ratio are changed. Results for Newtonian, shear thinning and viscoelastic constitutive equations show that, despite the multivalued nature of the slip model, multiplicity (and thus hysteresis) is absent at high L/D.  For the sake of completeness, we also carry out time-dependent simulations at constant piston speed taking fluid compressibility into account. These simulations show that oscillations in the pressure drop and exit volumetric flow rate result only if the system is operated in the multiplicity region of the steady state flow curve, in agreement with the results of similar simulations by researchers using various multivalued slip models without pressure dependence. The results demonstrate that a multivalued slip model does not guarantee multiplicity in the flow curve for the constant pressure drop operation, nor oscillations for constant piston speed operation. Received: 18 August 1997 Accepted: 30 March 1998     

Numerical simulation of entry flow of the IUPAC-LDPE melt

Numerical simulations have been undertaken for the creeping entry flow of a well-characterized polymer melt (IUPAC-LDPE) in a 4:1 axisymmetric and a 14:1 planar contraction. The fluid has been modeled using an integral constitutive equation of the K-BKZ type with a spectrum of relaxation times (Papanastasiou–Scriven–Macosko or PSM model). Numerical values for the constants appearing in the equation have been obtained from fitting shear viscosity and normal stress data as measured in shear and elongational data from uniaxial elongation experiments. The numerical solutions show that in the axisymmetric contraction the vortex in the reservoir first increases with increasing flow rate (or apparent shear rate), goes through a maximum and then decreases following the behavior of the uniaxial elongational viscosity. For the planar contraction, the vortex diminishes monotonically with increasing flow rate following the planar extensional viscosity. This kinematic behavior is not in agreement with recent experiments. The PSM strain-memory function of the model is then modified to account for strain-hardening in planar extension. Then the vortex pattern shows an increase in both axisymmetric and planar flows. The results for planar flow are compared with recent experiments showing the correct trend.