Tension enhancement in branched macromolecules upon adhesion on a solid substrate

TL;DR

This study uses Molecular Dynamics simulations to explore how adhesion to a surface induces tension in branched macromolecules, affecting bond scission, morphology, and degradation, with implications for material stability.

Contribution

It provides new insights into the tension distribution and degradation mechanisms of bottle-brush macromolecules adsorbed on surfaces, highlighting the effects of side chain length and adhesion strength.

Findings

Tension distribution varies along the backbone depending on grafting density.

Longer side chains can block each other at high adhesion, affecting stability.

Simulation results align qualitatively with experimental and theoretical predictions.

Abstract

The effect of self-generated tension in the backbone of a bottle-brush (BB) macromolecule, adsorbed on an attractive surface, is studied by means of Molecular Dynamics simulations of a coarse-grained bead-spring model in the good solvent regime. The BB-molecule is modeled as a backbone chain of $L$ beads, connected by breakable bonds and with side chains, tethered pairwise to each monomer of the backbone. Our investigation is focused on several key questions that determine the bond scission mechanism and the ensuing degradation kinetics: how are frequency of bond scission and self-induced tension distributed along the BB-backbone at different grafting density $\sigma_g$ of the side chains? How does tension $f$ depend on the length of the side chains $N$, and on the strength of surface adhesion $\epsilon_s$? We examine the monomer density distribution profiles across the BB-backbone at different $\epsilon_s$ and relate it to adsorption-induced morphological changes of the macromolecule whereby side chains partially desorb while the remaining chains spread better on the surface. Our simulation data are found to be in qualitative agreement with experimental results and recent theoretical predictions. Yet we demonstrate that the interval of parameter values where these predictions hold is limited in $N$. Thus, at high values of $\epsilon_s$, too long side chains mutually block each other and freeze effectively the bottle-brush molecule.