Systematic derivation of hydrodynamic equations for viscoelastic phase separation

TL;DR

This paper derives a comprehensive hydrodynamic two-fluid model for viscoelastic phase separation in polymer solutions, ensuring thermodynamic consistency and incorporating inertial, elastic, and interfacial effects from a molecular basis.

Contribution

It provides a systematic derivation of a viscoelastic phase separation model directly from molecular principles, including inertial effects and a novel rheological constitutive equation.

Findings

Model includes inertial and elastic effects.

Derives a rheological equation differing from Oldroyd-B.

Ensures thermodynamic consistency of the hydrodynamic equations.

Abstract

(abridged) We present a detailed derivation of a simple hydrodynamic two-fluid model, which aims at the description of the phase separation of non-entangled polymer solutions, where viscoelastic effects play a role. It is directly based upon the coarse-graining of a well-defined molecular model, such that all degrees of freedom have a clear and unambiguous molecular interpretation. The considerations are based upon a free-energy functional, and the dynamics is split into a conservative and a dissipative part, where the latter satisfies the Onsager relations and the Second Law of thermodynamics. The model is therefore fully consistent with both equilibrium and non-equilibrium thermodynamics. The derivation proceeds in two steps: Firstly, we derive an extended model comprising two scalar and four vector fields, such that inertial dynamics of the macromolecules and of the relative motion of the two fluids is taken into account. In the second step, we eliminate these inertial contributions and, as a replacement, introduce phenomenological dissipative terms, which can be modeled easily by taking into account the principles of non-equilibrium thermodynamics. The final simplified model comprises the momentum conservation equation, which includes both interfacial and elastic stresses, a convection-diffusion equation where interfacial and elastic contributions occur as well, and a suitably convected relaxation equation for the end-to-end vector field. In contrast to the traditional two-scale description that is used to derive rheological equations of motion, we here treat the hydrodynamic and the macromolecular degrees of freedom on the same basis. Nevertheless, the resulting model is fairly similar, though not fully identical, to models that have been discussed previously. Notably, we find a rheological constitutive equation that differs from the standard Oldroyd-B model. ...