Phase Coexistence in Thermoresponsive PNIPAM Hydrogels Triggered by Mechanical Forces

Poly-(<i>N</i>-isopropylacrylamide) (PNIPAM) is a temperature-responsive polymer that undergoes large volumetric deformations through a transition from a swollen to a collapsed state at a volume phase transition temperature (VPTT). Locally, these deformations stem from the coil-to-globule transition of individual chains. In this contribution, I revisit the study of SuzukiA., ; IshiiT., [J. Chem. Phys.1999, 110, 2289-2296], which demonstrated that a PNIPAM rod can exhibit phase coexistence (i.e., comprise swollen and collapsed domains simultaneously) near the VPTT when subjected to mechanical constraints. Specifically, that paper showed that (1) collapsed domains gradually form in a fixed swollen rod with time and (2) swollen domains can nucleate in a collapsed rod under uniaxial extension. These behaviors originate from the local thermo-mechanical response of the chains, which transition between states in response to the applied mechanical loading. Here, I develop a statistical-mechanics based framework that captures the behavior of individual chains below and above the VPTT and propose a probabilistic model based on the local chain response that sheds light on the underlying mechanisms governing phase nucleation and growth. The model is validated through comparison with experimental data. The findings from this work suggest that in addition to the classical approaches, in which the VPTT is programmed through chemical composition and network topology, the transition can be tuned by mechanical constraints. Furthermore, the proposed framework offers a pathway to actively tailor the VPTT through the exertion of mechanical forces, enabling improved control and performance of PNIPAM hydrogels in modern applications.