Accurate coarse-grained models for mixtures of colloids and linear polymers under good-solvent conditions

TL;DR

This paper develops and validates a coarse-grained modeling approach for mixtures of linear polymers and colloids, accurately capturing structural and thermodynamic properties under good-solvent conditions, especially for specific size ratios.

Contribution

The authors extend a polymer coarse-graining strategy to polymer-colloid mixtures, introducing a transferability-based approach for larger blob models and validating it against full-monomer simulations.

Findings

The tetramer model accurately predicts properties for q≤1.

The n=10 blob model improves accuracy for q=2.

Transferability assumptions enable larger blob models without extensive reparameterization.

Abstract

A coarse-graining strategy, previously developed for polymer solutions, is extended here to mixtures of linear polymers and hard-sphere colloids. In this approach groups of monomers are mapped onto a single pseudoatom (a blob) and the effective blob-blob interactions are obtained by requiring the model to reproduce some large-scale structural properties in the zero-density limit. We show that an accurate parametrization of the polymer-colloid interactions is obtained by simply introducing pair potentials between blobs and colloids. For the coarse-grained model in which polymers are modelled as four-blob chains (tetramers), the pair potentials are determined by means of the iterative Boltzmann inversion scheme, taking full-monomer pair correlation functions at zero-density as targets. For a larger number $n$ of blobs, pair potentials are determined by using a simple transferability assumption based on the polymer self-similarity. We validate the model by comparing its predictions with full-monomer results for the interfacial properties of polymer solutions in the presence of a single colloid and for thermodynamic and structural properties in the homogeneous phase at finite polymer and colloid density. The tetramer model is quite accurate for $q\lesssim 1$ ($q=\hat{R}_g/R_c$, where $\hat{R}_g$ is the zero-density polymer radius of gyration and $R_c$ is the colloid radius) and reasonably good also for $q=2$. For $q=2$ an accurate coarse-grained description is obtained by using the $n=10$ blob model. We also compare our results with those obtained by using single-blob models with state-dependent potentials.