"In silico" synthesis of microgel particles

TL;DR

This paper introduces a novel in silico methodology to assemble and simulate realistic microgel particles, enabling better theoretical understanding of their swelling behavior and structure under various conditions.

Contribution

A new assembly protocol for microgels using patchy particles under confinement, validated by reproducing experimental swelling curves and analyzing structural properties.

Findings

Successfully reproduced experimental swelling curves.

Demonstrated structural and swelling behavior consistent with the fuzzy sphere model.

Established a foundation for future elastic and interaction studies.

Abstract

Microgels are colloidal-scale particles individually made of crosslinked polymer networks that can swell and deswell in response to external stimuli, such as changes to temperature or pH. Despite a large amount of experimental activities on microgels, a proper theoretical description based on individual particle properties is still missing due to the complexity of the particles. To go one step further, here we propose a novel methodology to assemble realistic microgel particles "in silico". We exploit the self-assembly of a binary mixture composed of tetravalent (crosslinkers) and bivalent (monomer beads) patchy particles under spherical confinement in order to produce fully-bonded networks. The resulting structure is then used to generate the initial microgel configuration, which is subsequently simulated with a bead-spring model complemented by a temperature-induced hydrophobic attraction. To validate our assembly protocol we focus on a small microgel test-case and show that we can reproduce the experimental swelling curve by appropriately tuning the confining sphere radius, something that would not be possible with less sophisticated assembly methodologies, e.g. in the case of networks generated from an underlying crystal structure. We further investigate the structure (in reciprocal and real space) and the swelling curves of microgels as a function of temperature, finding that our results are well described by the widely-used fuzzy sphere model. This is a first step toward a realistic modelling of microgel particles, which will pave the way for a careful assessment of their elastic properties and effective interactions.