Coarse-grained Soft-Clusters Remain non-Diffusing in the Melt State

TL;DR

This study uses molecular dynamics simulations to explore the non-diffusing, cooperative glass state of large soft-clusters in melts, revealing unique 3D hierarchical dynamics distinct from chain-like polymers.

Contribution

It introduces the concept of cooperative glass in 3D soft-clusters, highlighting their non-diffusive behavior and divergent relaxation times, advancing understanding of glassy dynamics in complex polymers.

Findings

Soft-clusters with over 200 beads do not diffuse above their glass transition temperature.

Relaxation occurs at the bead level, but the clusters only rotate within cages.

The cooperative glass state persists up to temperatures ten times the glass transition temperature.

Abstract

Melts of 3-dimensional dendritic beads-springs, namely coarse-grained soft-clusters, are studied by molecular dynamics simulations. The goal is to elucidate the unique dynamics of giant molecules, or generally speaking, 3-dimensional architectured polymers. When constituted by more than the critical number around 200 beads, soft-clusters cannot diffuse or relax far above their glass transition temperature, although relaxation can happen on the level of beads. Each soft-cluster can only rotate in the cage formed by neighboring soft-clusters. Such a non-diffusing state would transform to the liquid state at exceptionally high temperature, e.g. 10 times the glass transition temperature. Agreeing with experiments, 3D hierarchies lead to unique dynamics, especially their divergent relaxation times with the number of beads. These unique dynamics are in sharp contrast with 1-dimensional chain-like polymers. We name such a special state as 'cooperative glass', because of the 'cooperation' of the 3D-connected beads. The design of soft-clusters may also resemble cooperative rearranging regions where cooperativeness is contributed by low temperature, thus offer further insights into the glass problem.