Electro-viscoelasticity of polymer melts in continuum theory

Abstract: Electro-viscoelastic theory for polymer melts has been extensively studied experimentally for the past century, primarily for manufacturing purposes. However, the modeling and theory for this have been minimal, leaving many questions on the mechanisms and behavior of an arbitrary flow scheme. To remedy this, previously solved overdamped Langevin equations for the Doi-Rouse model are modified to include charge and electric field potential forces. The charge sequence on the chain is hypothesized to be a cosine sequence along the chain, resembling multiple electric dipoles that conveniently correspond to a Rouse mode of the chain. These are then solved for the shear stress under homogeneous shear rates and electric fields to find directional viscosity increases depending on the shearing and electric field orientation. Using the newly derived shear stress from the Doi-Rouse approach, a continuum model is proposed that resembles a modified upper-convected Maxwell model, including polarization stresses in terms of an electric field dyadic. This new continuum model, named the upper-convected electro-Maxwell model, is verified using Kremer-Grest polymer chains simulated with molecular dynamics for multiple flow schemes and a specified charge sequence along the chain. Furthermore, the MD results verified the difference in the overall and charge sequence relaxation times through the shear and normal stress polarizations, showing the necessity for the upper-convected derivative of the electric field dyadic to correct the viscosity scaling. Finally, the dynamic properties of the polarized polymer melt are examined analytically, finding that the phase shift is unaffected by the electric field contribution.