Modeling of polymer phase transition from crystalline to conformationally disordered phase

TL;DR

This paper develops an analytical, physics-based model to describe the phase transition in polymers from crystalline to conformationally disordered phases, validated by molecular dynamics simulations of polyethylene.

Contribution

It introduces a novel analytical model capturing the phase transition mechanism, incorporating elastic and conformational contributions, and validates it against simulation data.

Findings

The model accurately predicts the transition temperature and pressure conditions.

Polyethylene exhibits a first-order phase transition characterized by increased gauche dihedral defects.

Model predictions align well with molecular dynamics simulation results.

Abstract

A physics-based analytical model describing the phase transition from crystalline to conformationally disordered (condis) crystalline phase is developed. In the model, the free energy is written as a function of temperature and the lattice parameter (mean distance between neighboring chains). It consists of two contributions: elastic and conformational. The elastic contribution describes the interaction between neighboring chains, while the conformational part takes into account the conformation of one chain inside the potential tube, formed by the neighboring chains. To verify this approach, polyethylene - the simplest polymer possessing the condis phase - was chosen as a modeling object. Previous experiments and molecular dynamics simulations show that the typical conformation of a polymer chain in a crystalline phase consists mainly of trans dihedrals and a small fraction of gauche dihedrals, which can be considered as defects of the crystalline lattice. These defects displace the chain inside the tube thus increasing the potential energy. The energy required to form such a defect decreases rapidly with increasing distance between neighboring chains. This leads to a first-order phase transition at a certain temperature to the condis phase, in which distance between neighboring chains is large and a fraction of gauche dihedrals is high. This physical picture of the phase transition is described by the proposed analytical model, the parameters of which were calibrated against the results of molecular dynamics simulations for atmospheric pressure. The model predictions for the pressure of 500 atm and 1000 atm are in perfect agreement with the results of molecular dynamics simulations.