Thermal Degradation of Unstrained Single Polymer Chain: Non-linear Effects at Work

TL;DR

This study uses Molecular Dynamics simulations to analyze how unstrained polymer chains break under heat, revealing different behaviors in inertial versus damped regimes, and showing that chain rupture follows Arrhenian temperature dependence with inhomogeneous bond rupture patterns.

Contribution

It provides new insights into the non-linear effects and inhomogeneous rupture dynamics of polymers during thermal degradation, including bond healing and fragmentation kinetics.

Findings

Chain rupture time follows Arrhenian behavior with temperature.

Rupture rate depends inversely on the number of bonds.

Degradation characterized as a first order reaction.

Abstract

We examine the thermally-induced fracture of an unstrained polymer chain of discrete segments coupled by an anharmonic potential by means of Molecular Dynamics simulation with a Langevin thermostat. Cases of both under- and over-damped dynamics are investigated, and a comparison with recent studies of bond scission in model polymers with harmonic interactions is performed. We find that the polymer degradation changes qualitatively between the inertial regime and that of heavily damped dynamics. The role of bond healing (recombination) is also studied and probability distributions for the recombination times and overstretched bond lengths are obtained. Our extensive simulations reveal many properties of the scission dynamics in agreement with the notion of random breakdown of independent bonds, e.g., the mean time of chain rupture, $<\tau>$ follows an Arrhenian behavior with temperature $T$, and depends on the number of bonds $N$ in the polymer as $<\tau> \propto N^{-1}$. In contrast, the rupture rates of the individual bonds along the polymer backbone indicate clearly the presence of self-induced inhomogeneity resulting from the interplay of thermal noise and nonlinearity. Eventually we examine the fragmentation kinetics during thermolysis. We demonstrate that both the probability distribution function of fragment sizes as well as the mean length of fragments at subsequent times $t$ characterize degradation as predominantly a first order reaction.