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arXiv · 2407.05401

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

William S. Fall·Henricus H. Wensink
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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.

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William S. Fall, Henricus H. Wensink. 2024-07-07. Complex Smectic Phases in Polymer Grafted Shape-Uniform Cellulose Nano-Crystals. https://doi.org/10.1021/acs.macromol.4c00205

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