Relaxation dynamics, Softness and Fragility of Microgels with Interpenetrated Polymer Networks

TL;DR

This study explores how the softness of interpenetrated polymer network microgels influences their relaxation dynamics and fragility, revealing a crossover in behavior and different diffusion mechanisms as concentration varies.

Contribution

It demonstrates how tuning PAAc content in IPN microgels affects their fragility and uncovers a dynamical crossover with distinct diffusion regimes using scattering techniques.

Findings

Dynamical crossover at a critical concentration.

Transition from super-Arrhenius to sub-Arrhenius relaxation.

Different diffusion mechanisms identified (Fickian, anomalous, ballistic).

Abstract

Microgels are elastic and deformable particles with a hybrid nature between that of polymers and colloids and unconventional behaviours with respect to hard colloids. We investigated the dynamics of a soft microgel made of interpenetrated polymer networks of PNIPAM and PAAc by means of coherent X-ray and light scattering techniques. By varying the particle softness through PAAc content we can tune at wish the fragility of IPN microgels. Interestingly we find the occurrence of a dynamical crossover at a critical weight concentration which leads to an evolution of the structural relaxation time from a super-Arrhenius to a slower than Arrhenius behaviour, a minimum for the shape parameter of intensity autocorrelation function and the emerging of distinct anomalous mechanisms for particle motion. This complex phenomenology can be described by a Fickian diffusion at very low concentrations, an effective non Fickian anomalous diffusion at intermediate values and a ballistic motion well described within the Mode Coupling Theory.