Influence of a nanoparticle on the structure and dynamics of model ionomer melts

We simulate a single spherical nanoparticle (NP) surrounded by partially neutralized ionomers. The coarse-grained ionomers consist of a linear backbone of neutral monomer beads with charged pendant beads and counterions, along with pendant 'sticker' beads that represent unneutralized acid groups. Two different NP interactions are considered; one in which the NP interacts uniformly with all beads in the system (neutral NP) and another in which the NP has higher cohesive interactions with ions and stickers (sticky NP). Ions are depleted around the neutral NP relative to the bulk, but are denser around the surface of the sticky NP. The bond vector autocorrelation function was computed as a function of distance from the NP. For the neutral NP, due to the absence of ions, there is an increase in bond rotational dynamics near the surface relative to the bulk, while the reverse trend is observed in the case of the sticky NP. These analyses were done systematically for differing mole content of pendants, levels of neutralization, and NP sizes; lower pendant content causes a significantly larger difference in the bond dynamics near and far from the NP surface.