Mass and Heat Diffusion in Ternary Polymer Solutions: A Classical Irreversible Thermodynamics Approach

TL;DR

This paper derives comprehensive governing equations for mass and heat diffusion in ternary polymer solutions using classical irreversible thermodynamics, highlighting the importance of cross-diffusion coefficients for accurate phase behavior modeling.

Contribution

It introduces a detailed 3x3 diffusion matrix framework based on Onsager relations, linking diffusion coefficients to chemical potential derivatives, and emphasizes the necessity of cross-diffusion terms.

Findings

Derived spinodal curves from the equations

Validated the positivity of entropy production constraints

Showed that ignoring cross-diffusion coefficients leads to incorrect phase behavior

Abstract

Governing equations for evolution of concentration and temperature in three-component systems were derived in the framework of classical irreversible thermodynamics using Onsager variational principle and were presented for solvent/solvent/polymer and solvent/polymer/polymer systems. The derivation was developed from the Gibbs equation of equilibrium thermodynamics using the local equilibrium hypothesis, Onsager reciprocal relations and Prigogine theorem for systems in mechanical equilibrium. It was shown that the details of mass and heat diffusion phenomena in a ternary system are completely expressed by a 3x3 matrix whose entries are mass diffusion coefficients (4 entries), thermal diffusion coefficients (2 entries) and three entries that describe the evolution of heat in the system. The entries of the diffusion matrix are related to the elements of Onsager matrix that are bounded by some constraints to satisfy the positive definiteness of entropy production in the system. All the elements of diffusion matrix were expressed in terms of derivatives of exchange chemical potentials of the components with respect to concentration and temperature. The spinodal curves of ternary polymer solutions were derived from the governing equations and their correctness was checked by the Hessian of free energy density. Moreover, it was proved that setting cross-diffusion coefficients to zero results in a contradiction, and, the governing equations without cross-diffusion coefficients do not express the actual phase behavior of the system.