Stiffness-dependent Dielectric Relaxation in Thermoreversible Microgels: Effects of Temperature and Strain

Abstract

We investigate how particle stiffness governs length-scale-dependent relaxation dynamics in dense suspensions of thermoresponsive PNIPAM microgels subjected to temperature variations and large amplitude oscillatory shear. By combining dielectric spectroscopy with rheometric measurements, we directly correlate microscopic polarization fluctuation dynamics with macroscopic mechanical relaxation. Highly crosslinked, stiffer microgels exhibit longer dielectric relaxation times across a broad temperature range and strain-induced slowing down, whereas softer, open-network microgels exhibit nearly strain-independent dielectric dynamics. Below the volume phase transition temperature (VPTT), macroscopic bulk stress relaxation experiments reveal that suspensions of the softest particles relax most rapidly. For the stiffer microgel suspensions, however, the dynamics decouple: bulk stress relaxation speeds up with increasing stiffness even as dielectric relaxation slows down. Above the VPTT, softer particles undergo greater volume collapse, leading to very rapid bulk stress relaxation. Besides exhibiting slower stress decay, stiffer microgel suspensions also undergo shear-induced structural regeneration during the later stages of deformation. These findings demonstrate that particle stiffness and internal architecture govern relaxation pathways across microscopic and macroscopic length scales, thereby providing a framework for designing adaptive soft metamaterials, stress-dissipative coatings, and self-healing robotic materials.