Unoccupied space and short-range order characterization in polymers under heat treatment

TL;DR

This study uses molecular dynamics simulations to analyze how heat treatment affects unoccupied space and short-range order in polyvinyl alcohol, revealing that annealing reduces free volume while quenching increases it.

Contribution

It introduces a computational approach combining Voronoi tessellation and open-source software to quantify free volume and order in polymers under different heat treatments.

Findings

Annealing reduces free volume content in PVA.

High cooling rates increase free volume in PVA.

Short-range order is more pronounced in annealed samples.

Abstract

Large scale molecular dynamics simulations on polyvinyl alcohol were used to investigate the distribution of unoccupied space under different heat treatments. Representative volume elements consisting of 3600 chains of 300 monomers were equilibrated at melt state and cooled by different cooling rates. The positions of center of mass of the monomers were extracted and a series of spatial analysis were conducted to estimate the distribution of free volume or unoccupied space by Voronoi tessellation algorithm. An open-source software was employed which incorporates both compilers of Matlab and C programing languages to reduce the computational costs associated with Voronoi calculations and statistical analysis. The results confirmed that low free volume content is achievable through annealing while high free volume content is achievable through quenching samples at high cooling rates. An appreciable degree of short-range order in the packing of chains is revealed in annealed samples.