Crystallization in melts and poor-solvent solutions of semiflexible polymers: extensive DPD study

TL;DR

This study uses dissipative particle dynamics simulations to investigate how crystallization in melts and poor-solvent solutions of semiflexible polymers depends on concentration, revealing the effects on crystalline fraction, crystallization speed, and crystallite size.

Contribution

It provides new insights into the crystallization behavior of semiflexible polymers in poor solvents, highlighting the influence of polymer concentration on crystallinity and crystallite growth.

Findings

Crystalline fraction decreases with increasing polymer volume fraction.

Crystallization speed remains nearly constant above 50% polymer concentration.

Maximum crystallite size occurs at approximately 90% polymer volume fraction.

Abstract

In the present work, crystallization in melts and poor-solvent solutions of semiflexible polymers with different concentration was studied by means of dissipative particle dynamics simulation technique. We use a coarse-grained polymer model trying to catch general principles of crystallization in such systems on large time and length scales. We observe the crystallization process starting from an initial randomly prepared system with different polymer volume fractions in a poor solvent. Because the solvent is very poor, the macrophase polymer-solvent separation takes place very fast and is accompanied by partial polymer crystallization. We have found that the overall crystalline fraction at the end of crystallization process decreases upon increasing the polymer volume fraction in the initial randomly prepared system, while the steady-state crystallization speed is almost the same at polymer volume fractions larger than 50\%. At the same time, the average crystallite size differs considerably and has a maximum value in the systems with 90\% polymer volume fraction. We assume that this polymer concentration is an optimal value in a sense of a balance between the amount of polymer material available for increasing crystallite size and chain entanglements preventing crystallites growth and merging.