Influence of chain topology and bond potential on the glass transition of polymer chains simulated with the bond fluctuation model

TL;DR

This study uses the bond fluctuation model with bond potential to explore how chain topology and bond strength influence the glass transition and crystallization behavior of polymer chains, revealing effects of branching and bond potential on vitrification.

Contribution

It introduces a variable bond potential factor B into the bond fluctuation model to systematically study its impact on polymer glass transition and crystallization, including branched chains.

Findings

Higher B values increase vitrification tendency.

Branched chains more readily crystallize and show multiple glass transitions.

Bond potential strength influences glass transition and crystallization behaviors.

Abstract

The bond fluctuation model with a bond potential has been applied to investigation of the glass transition of linear chains and chains with a regular disposition of small branches. Cooling and subsequent heating curves are obtained for the chain energies and also for the mean acceptance probability of a bead jump. In order to mimic different trends to vitrification, a factor B gauging the strength of the bond potential with respect to the long-range potential (i.e. the intramolecular or intermolecular potential between indirectly bonded beads) has been introduced. (A higher value of B leads to a preference for the highest bond lengths and a higher total energy, implying a greater tendency to vitrify.) Different cases have been considered for linear chains: no long-range potential, no bond potential and several choices for B. Furthermore, we have considered two distinct values of B for alternate bonds in linear chains. In the case of the branched chains, molecules with different values of B for bonds in the main chain and in the branches have also been investigated. The possible presence of crystallization has been characterized by calculating the collective light scattering function of the different samples after annealing at a convenient temperature below the onset of crystallization. It is concluded that crystallization is inherited more efficiently in the systems with branched chains and also for higher values of B. The branched molecules with the highest B values in the main chain bonds exhibit two distinct transitions in the heating curves which may be associated with two glass transitions. This behavior has been detected experimentally for chains with relatively long flexible branches.