The transition from highly to fully stretched polymer brushes in good solvent

TL;DR

This study uses Monte Carlo simulations to explore how polymer brushes transition from a highly stretched to a fully stretched state at high grafting densities, revealing deviations from classical theory and a rapid conformational change.

Contribution

It provides new insights into the conformational transition of polymer brushes at high grafting densities, challenging existing self-consistent field theory predictions.

Findings

Monomer density profiles deviate from parabolic form at high densities.

A rapid transition from parabolic to fully stretched polymers is observed.

Significant change in end-monomer height distribution and brush height slope occurs.

Abstract

The stretching of brushes of long polymers grafted to a planar surface is investigated byMonte Carlo simulations in the limit of very high grafting densities, as achieved in recent experiments. The monomer density profiles are shown to deviate considerably from the parabolic limiting form predicted by self-consistent field theory. A rapid transition is observed from parabolic to fully stretched polymers, characterized by a dramatic change in the end-monomer height distribution and by a clear cross-over in the slope of the brush height versus scaled grafting density.