A Novel Design Strategy for Fully Physically Linked Double Network Hydrogels with Tough, Fatigue Resistant, and Self‐Healing Properties

TLDR

Double‑network hydrogels linked covalently are the toughest known, yet they lack fatigue resistance and self‑healing because irreversible covalent bonds break. This work proposes a design strategy to enhance both fatigue resistance and self‑healing of DN gels by incorporating a ductile, hydrophobically interacting second network. The authors synthesize fully physically cross‑linked Agar/HPAAm DN gels in a single‑pot reaction, creating a hydrophobic polyacrylamide network that associates with agar. The resulting Agar/HPAAm DN gels show mechanical strength and toughness comparable to conventional DN gels, while also exhibiting rapid self‑recovery, strong fatigue resistance, and self‑healing at room temperature, offering new insights into DN hydrogel structure‑property relationships.

Abstract

Double network (DN) hydrogels with two strong asymmetric networks being chemically linked have demonstrated their excellent mechanical properties as the toughest hydrogels, but chemically linked DN gels often exhibit negligible fatigue resistance and poor self‐healing property due to the irreversible chain breaks in covalent‐linked networks. Here, a new design strategy is proposed and demonstrated to improve both fatigue resistance and self‐healing property of DN gels by introducing a ductile, nonsoft gel with strong hydrophobic interactions as the second network. Based on this design strategy, a new type of fully physically cross‐linked Agar/hydrophobically associated polyacrylamide (HPAAm) DN gels are synthesized by a simple one‐pot method. Agar/HPAAm DN gels exhibit excellent mechanical strength and high toughness, comparable to the reported DN gels. More importantly, because the ductile and tough second network of HPAAm can bear stress and reconstruct network structure, Agar/HPAAm DN gels also demonstrate rapid self‐recovery, remarkable fatigue resistance, and notable self‐healing property without any external stimuli at room temperature. In contrast to the former DN gels in both network structures and underlying association forces, this new design strategy to prepare highly mechanical DN gels provides a new avenue to better understand the fundamental structure‐property relationship of DN hydrogels, thus broadening current hydrogel research and applications.