Numerical insights on the volume phase transition of thermoresponsive hollow microgels

TL;DR

This study uses molecular dynamics simulations to analyze the swelling behavior of hollow microgels during the volume phase transition, revealing key insights into cavity filling and size discontinuities relevant for applications.

Contribution

It provides a detailed computational characterization of hollow microgel swelling, including the onset of cavity filling and the relationship with the volume phase transition, validated against experimental data.

Findings

Discontinuity in radius of gyration at VPT under certain conditions

Absence of discontinuity in hydrodynamic radius matches experiments

Established a minimal stable hollow microgel model for future studies

Abstract

Hollow microgels, consisting of a pNIPAM polymer network with a central cavity, have significant potential due to their tunable softness and encapsulation capabilities. Using molecular dynamics simulations, we thoroughly characterise the swelling behaviour of neutral hollow microgels across the Volume Phase Transition (VPT) upon varying crosslinker concentration, shell thickness, and size. In particular, we examine in detail the onset of cavity filling and its relation to the VPT, detecting the presence of a discontinuity in the radius of gyration of the microgels, if an appropriate balance between shell stiffness and thermoresposiveness is reached. The discontinuity is, however, absent in the behaviour of the hydrodynamic radius, in agreement with experimental observations. We then test our numerical model by direct comparison of form factors with available measurements in the literature and also establish a minimal-size, stable hollow microgel for future computationally feasible bulk investigations. Overall, our findings provide valuable insights into the fundamental swelling properties of hollow microgels that can be useful to control the opening and closing of the cavity for application purposes.