The origins, uses and evaluation of constitutive equations for the stress tensor of polymeric liquids are discussed.

Constitutive equations for polymeric liquids

Results of nonequilibrium molecular dynamics computer simulations of a planar Couette flow are presented for the multibead anharmonic‐spring model. The finitely extensible nonlinear elastic force law is used to connect the up to 100 beads of a chain molecule. Rheological data (shear viscosity, normal pressure differences) are discussed and compared with quantities describing the chain conformation (e.g., alignment tensor, static structure factor). This renders possible a test of the theoretical approaches which connect these quantities. In agreement with recent experiments, the static strucure factor exhibits characteristic elliptical distortions of the polymer coil whose magnitude depends on the distance from the gyration center. In our simulations the zero‐shear‐rate viscosity is found to scale linearly with the number of beads N up to chains with N=60. A weak upturn of the viscosity per bead for N=100 is found which may indicate the onset of the reptation regime.

Rheology and structural changes of polymer melts via nonequilibrium molecular dynamics

The molecular stress function theory for polymer melts is extended to include a new, dissipative convective constraint release process. First the Helmholtz free energy of tube segments with strain-dependent tube diameter is established neglecting constraint release, and it is demonstrated that the molecular stress is a function of the average logarithmic stretch under these conditions. Then convective constraint release is introduced as a dissipative process in the energy balance of tube deformation, which leads to a strain-dependent evolution equation for the molecular stress function. Constraint release is considered to be the consequence of different convection mechanisms for tube orientation and tube cross section. Our new, dissipative constraint release model emphasizes that tube kinematics are fundamentally different for rotational and nonrotational flows, and therefore distinguishes explicitly between simple shear and pure shear (planar extension). For the startup of simple shear and extensional flows, the predictions of our set of constitutive equations consisting of a history integral for the stress tensor and a differential evolution equation for the molecular stress function with only two nonlinear material parameters are in excellent agreement with experimental data of a polydisperse high-density polyethylene (HDPE) and a polydisperse low-density polyethylene (LDPE) melt. Also, stress relaxation after step-shear strain is described for both the HDPE and the LDPE melt.

The molecular stress function model for polydisperse polymer melts with dissipative convective constraint release

In order to study the rheology of long chain branched polymers, branches have been added on linear polypropylene precursors in varying amounts using reactive modification with peroxydicarbonates. The branched polypropylene samples show distinct strain hardening, something absent from the linear melt; this considerably improves the melt strength of the modified polymer. The zero shear viscosity and the elasticity measured by the relaxation spectrum also increase with the number of branches per molecule. Two models are applied to describe strain hardening of the viscosity during the course of elongation. The model parameters were found to vary systematically with the degree of branching and, therefore, their values can be used as a measure of this. Consequently, fluidity, elasticity, strain hardening, and melt strength are all related to the degree of long chain branching.

Effect of long branches on the rheology of polypropylene

The seminal ideas of de Gennes and Doi and Edwards have provided the theoretical framework for much of the recent effort to model the rheological behavior of entangled polymer melts and solutions. Recent theoretical work has incorporated a number of important additions to the basic Doi-Edwards theory, including an explicit description of chain stretch and additional relaxation mechanisms such as contour length fluctuations (CLF) and convective constraint release (CCR). However, very little quantitative data has been published on the rheological behavior of entangled systems in strong flows. Hence, a comprehensive examination of the theoretical developments has not been possible. The experiments described in this paper use the filament stretching rheometer to obtain transient extensional stress growth data and steady state uniaxial extensional viscosity data for a number of entangled, narrow molecular weight distribution polystyrene solutions in the strain-rate regime characterized by a significant degree of both chain alignment and stretch. These results are then compared with theoretical predictions for a number of the current generation of reptation-based models, including mechanisms for chain stretching, contour length fluctuations, and convective constraint release. These comparisons demonstrate that when the model parameters are properly obtained from linear viscoelastic measurements, the recent model due to Mead, Larson, and Doi (Macromolecules 1998, 31, 7895) provides quantitative predictions for this class of flows for solutions spanning the complete range from very lightly to highly entangled solutions.

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Extensional Rheometry of Entangled Solutions

From stress-strain experiments in extensional and shearing flows, nonlinear strain measures and effective damping functions are derived for a polyisobutylene melt. The strain measures determined in planar extensional flow and in simple shear flow coincide. Experimental results are compared with predictions of two molecular theories, the Doi-Edwards model and the molecular stress function approach of Wagner and Schaeffer. Discrepancies between theories and experiment lead to a reconsideration of the classification of extensional flows. The symmetry of the flow field is identified and quantified as an important parameter influencing the strain measure, and a unifying strain measure for general extensional and shearing flows of polymer melts is presented.

Assessment of nonlinear strain measures for extensional and shearing flows of polymer melts

Allowing for flow-dependent slip in the junctions of a temporary junction network, we derive the constitutive equations of temporary slip-link networks. The stress tensor is determined by three material functions, namely, the time-dependent linear-viscoelastic memory function, and two strain-dependent functions describing slip and disentanglement of network strands. Slip and disentanglement are related via a mass balance for network strands.

J. Schaeffer

Papers

Assessment of nonlinear strain measures for extensional and shearing flows of polymer melts

Constitutive equations from Gaussian slip-link network theories in polymer melt rheology