Water-responsive shape-memory polymers (SMPs) are desirable for biomedical applications, but their limited shape recovery process is problematic. Herein, we demonstrate a shape-memory poly(vinyl alcohol) (SM-PVA) with programmable multistep shape recovery processes in water via a wettability contrast strategy. A hexamethyldisilazane (HMDS)-treated SiO2 nanoparticle layer with varying loading weights was rationally deposited onto the surface of SM-PVA, aiming to create surface-wettability contrast. The varying wettability led to different water adsorption behaviors of SM-PVA that could be well-described by the pseudo-first-order kinetic model. The results calculated from the kinetic model showed that both the pseudo-first order-adsorption rate constant and the saturated water absorption of SM-PVA demonstrated a declining trend as the loading weight of SiO2 increased, which laid the foundation for the local regulation of the water-responsive rate of SM-PVA. Finally, two proof-of-concept drug-delivery devices with diverse three-dimensional structures and actuations are presented based on the water-responsive SM-PVA with preprogrammed multistep shape recovery processes. We believe the programmable shape-memory behavior of water-responsive SM-PVA could highly extend its use in drug delivery, tissue engineering scaffolds, and smart implantable devices, etc.
Keywords: shape recovery process; shape-memory polymer; smart materials; water-responsive; wettability contrast.