Heirarchical and synergistic self-assembly in composites of model Wormlike micellar-polymers and nanoparticles results in nanostructures with diverse morphologies

TL;DR

This study uses Monte Carlo simulations to explore how nanoparticles and equilibrium polymers self-assemble into diverse nanostructures, revealing morphological transitions driven by polymer density and interaction parameters.

Contribution

It demonstrates the morphological transitions and shape anisotropy in nanoparticle-polymer composites resulting from synergistic self-assembly, providing a theoretical understanding of diverse nanostructures.

Findings

Nanoparticle aggregates transition from network-like to cluster structures.

Polymer matrix shifts from dispersed to percolating network.

Nanocluster shapes depend on polymer density and interaction parameters.

Abstract

Using Monte Carlo simulations, we investigate the self-assembly of model nanoparticles inside a matrix of model equilibrium polymers (or matrix of Wormlike micelles) as a function of the polymeric matrix density and the excluded volume parameter between polymers and nanoparticles. In this paper, we show morphological transitions in the system architecture via synergistic self-assembly of nanoparticles and the equilibrium polymers. In a synergistic self-assembly, the resulting morphology of the system is a result of the interaction between both nanoparticles and the polymers, unlike the polymer templating method. We report the morphological transition of nanoparticle aggregates from percolating network-like structures to non-percolating clusters as a result of the change in the excluded volume parameter between nanoparticles and polymeric chains. In parallel with the change in the self-assembled structures of nanoparticles, the matrix of equilibrium polymers also shows a transition from a dispersed state to a percolating network-like structure formed by the clusters of polymeric chains. We show that the shape anisotropy of the nanoparticle clusters formed is governed by the polymeric density resulting in rod-like, sheet-like or other anisotropic nanoclusters. It is also shown that the pore shape and the pore size of the porous network of nanoparticles can be changed by changing the minimum approaching distance between nanoparticles and polymers. We provide a theoretical understanding of why various nanostructures with very different morphologies are obtained.