Molecular Modeling and Simulation of Polymer Nanocomposites with Nanorod Fillers

SZ Lu and ZJ Wu and A Jayaraman, JOURNAL OF PHYSICAL CHEMISTRY B, 125, 2435-2449 (2021).

DOI: 10.1021/acs.jpcb.1c00097

We present a coarse-grained (CG) molecular dynamics (MD) simulation study of polymer nanocomposites (PNCs) containing nanorods with homogeneous and patchy surface chemistry/functionalization, modeled with isotropic and directional nanorod-nanorod attraction, respectively. We show how the PNC morphology is impacted by the nanorod design (i.e., aspect ratio, homogeneous or patchy surface chemistry/functionalization) for nanorods with a diameter equal to the Kuhn length of the polymer in the matrix. For PNCs with 10 vol % nanorods that have an aspect ratio <= 5, we observe percolated morphology with directional nanorod-nanorod attraction and phase-separated (i.e., nanorod aggregation) morphology with isotropic nanorod-nanorod attraction. In contrast, for nanorods with higher aspect ratios, both types of attractions result in aggregated nanorods morphology due to the dominance of entropic driving forces that cause long nanorods to form orientationally ordered aggregates. For most PNCs with isotropic or directional nanorod-nanorod attractions, the average matrix polymer conformation is not perturbed by the inclusion of up to 20 vol % nanorods. The polymer chains in contact with nanorods (i.e., interfacial chains) are on average extended and statistically different from the conformations the matrix chains adopt in the pure melt state (with no nanorods); in contrast, the polymer chains far from nanorods (i.e., bulk chains) adopt the same conformations as the matrix chains adopt in the pure melt state. We also study the effect of other parameters, such as attraction strength, nanorod volume fraction, and matrix chain length, for PNCs with isotropic or directional nanorod-nanorod attractions. Collectively, our results provide valuable design rules to achieve specific PNC morphologies (i.e., dispersed, aggregated, percolated, and orientationally aligned nanorods) for various potential applications.

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