Complex Smectic Phases in Polymer Grafted Shape-Uniform Cellulose Nano-Crystals

TL;DR

This study uses molecular dynamics simulations to explore how short chain grafting affects liquid crystalline phases in cellulose nano-crystals, revealing complex phase behavior influenced by grafting density.

Contribution

It uncovers novel liquid crystal phase transitions in grafted nano-rods that challenge existing models of rod-like liquid crystal systems.

Findings

Grafting density non-trivially alters LC phases.

Grafted CNCs show suppression and re-emergence of Smectic phases.

New phase behaviors outside current theoretical descriptions.

Abstract

The effect of short chain grafting on the liquid crystalline (LC) ordering of nano-crystals is investigated using molecular dynamics simulations of a coarse-grained grafted nano-rod model. Monodisperse nano-rods, with aspect ratios typical of cellulose nano-crystals (CNCs) are grafted randomly with oligomers at different grafting densities. LC ordering depends non-trivially on grafting density as the effective nano-rod shape and softness is modified. Ungrafted rods exhibit Nematic and tilted Smectic-C phases. At 25\% grafting, the addition of a few side chains entirely suppresses Smectic order and instead a persistent Nematic phase is favoured. Intermediary grafting, around 50\%, results in a Nematic and the reappearance of tilted Smectic-F phases. Heavier grafting facilitates direct transitions to either Smectic-I with extreme tilt (75\%) or an un-tilted Smectic-B (100\%). Such behaviour falls outside of current hard or soft-rod descriptions of phase-transitions in rod-like LC systems and points to undiscovered LC behaviour in both shape-purified grafted/un-grafted CNCs.