We present a new coarse-grained (CG) model that captures directional interactions between graft and matrix polymer chains in polymer nanocomposites (PNCs) comprising polymer grafted spherical nanoparticles in a matrix polymer. In this CG model we incorporate acceptor and donor CG beads along with graft and matrix monomer CG beads and optimize the bonded and nonbonded interactions to mimic directional and specific H-bonding between the acceptor and donor sites on graft and matrix chains, respectively. Using this CG model and molecular dynamics simulations we show that H-bonding interactions between graft and matrix polymer chains increase the grafted layer wetting by matrix chains compared to that at the purely entropic limit. One can achieve equivalent grafted layer wetting in PNCs with directional acceptor–donor interactions and PNCs with isotropic graft–matrix interactions, but the directional acceptor–donor interaction strength needs to be much stronger than the isotropic graft–matrix monomer attraction strength. Strikingly, despite equivalent grafted layer wetting and graft chain conformations, on average, each graft chain interacts with fewer matrix chains and has a lower free volume in PNCs with H-bonding interaction as compared to PNCs with isotropic graft-matrix attraction. These trends are seen both at high (brush-like) and low grafting densities, and in PNCs with equal graft and matrix chain lengths as well as PNCs with matrix chain length three times the graft chain length.

We use Langevin dynamics simulations and Polymer Reference Interaction Site Model (PRISM) theory to study polymer grafted nanoparticles specifically to explain the impact of comb polymer architecture on the grafted layer structure and effective interparticle interactions in solvent and in matrix polymer. First, we use simulations to study a single particle grafted with comb polymers with varying comb polymer design (i.e., spacing and length of side chains along the comb polymer backbone), grafting density (i.e., polymer chains/particle surface area), and particle curvature in implicit solvent at the athermal limit. We find that increasing side chain length or decreasing side chain spacing along the comb polymer effectively swells and extends the polymer backbone due to the increasing side chain monomer crowding. For particles at finite curvature with increasing side chain monomer crowding, the monomer concentration profile of the comb polymer backbone at short distances from the surface resembles the concentration profile of a semiflexible linear polymer and at farther distances resembles that of flexible linear polymers grafted to a flat surface. As the particle curvature decreases to zero (i.e., flat surface), increasing side chain crowding has a simpler effect of expanding the grafted layer without changing the overall shape of the concentration profile. To understand how architecture affects the interactions of the comb polymer grafted particles, we use PRISM theory to calculate the potential of mean force (PMF) between comb polymer grafted particles in implicit solvent, explicit solvent, and explicit matrix of athermal linear polymers. On the basis of the PMFs calculated for a wide range of design parameters (grafting density, comb polymer design), we find that, compared to linear polymers, the comb polymers exhibit stronger effective attraction in the PMF between the grafted particles in both small molecule solvent and polymer matrix due to the increased crowding in the grafted layer from the comb polymer side chains. Interestingly, the PMF between the grafted particles in a small molecule solvent is more sensitive to the comb polymer design (i.e., side chain length and spacing) than the PMF between the grafted particles in a polymer matrix.

Active swimmers are known to accumulate along external boundaries owing to their persistent self-motion, resulting in a significant reduction in their effective mobility through heterogeneous and tortuous materials. The dynamic interplay between the slowdown experienced by the active constituents near boundaries and their long-time diffusivity is critical for understanding and predicting active transport in porous media. In this work, we study the impact of boundary layer accumulation on the effective diffusivity of active matter by analyzing the motion of active Brownian particles in an array of fixed obstacles. We combine Janus particle experiments, Brownian dynamics simulations, and a theoretical analysis based on the Smoluchowski equation. We find that the shape, curvature, and microstructure of the obstacles play a critical role in governing the effective diffusivity of active particles. Indeed, even at dilute packing fractions of obstacles, ϕ = 12%, we observed a 25% reduction in the effective diffusivity of active particles, which is much larger than the hindrance experienced by passive Brownian particles. Our combined experimental and computational results demonstrate a strong coupling between the active force and the porous media microstructure. This work provides a framework to predict and control the transport of active matter in heterogeneous materials.

Physical boundaries play a key role in governing the overall transport properties of nearby self-propelled particles. In this work, we develop dispersion theories and conduct Brownian dynamics simulations to predict...