Self-assembly of polymer-grafted nanoparticles in solvent-free conditions

Grafting of polymer chains onto the surface of spherical nanoparticles leads to a hybrid type of fluid that exhibits properties of both particle suspensions and melts of star polymers-these properties being controlled by the relative dimensions of the grafted polymer chains to the nanoparticle diameter, D, and the number of the number of chains grafted on the nanoparticle surface, f. While polymer-grafted nanoparticles (GNP) of this kind typically have a spherical average shape after grafting even a moderate number of chains, their instantaneous molecular shape can fluctuate significantly due to the deformation of the grafted chains. Both simulations and measurements have previously revealed that these "conformationally polarizable" particles can exhibit self-assembly into large scale polymeric structures in both solution and in polymer melts, and we simulate polymer-grafted nanoparticles with D and temperature (T) variations without a dispersing solvent to better understand the nature of this self-assembly process. We observe a reversible self-assembly into linear and branched dynamic GNP structures, where the extent of the assembly and geometry depend on D and T, and we constructed a map capturing the GNP structural behavior with D and T variations. Since the shape of the GNPs appeared to be correlated with the occurrence of the GNP self-assembly, we quantified the average shape and a measure of shape fluctuations to better understand how molecular shape influences their propensity to self-assemble into different structural forms. Based on this framework, we describe the clustering process of the GNPs as an equilibrium polymerization phenomenon and we calculate the order parameter governing the dynamic clustering behavior of GNPs, the average mass of the clusters, size distribution, and the apparent fractal dimension of the clusters.