Selected Phase Separation Renders High Strength and Toughness to Polyacrylamide/Alginate Hydrogels with Large-Scale Cross-Linking Zones
Chongzhi Xu, Xiansheng Zhang, Shuo Liu, Xianwei Zhao, Cunzhen Geng, Lili Wang, Yanzhi Xia
Abstract
High water content usually contradicts the mechanics for hydrogels, and achieving both characteristics is extremely challenging. Herein, a novel confined-chain-aggregation (CCA) strategy is developed to fabricate ultrastrong and tough hydrogels without sacrificing their inherent water capacity. Based on the popular polyacrylamide/alginate (PAAm/Alg) system with a double network (DN), a poor solvent exchange is induced once PAAm is fully cross-linked but prior to ionic cross-linking of alginate. In this case, the alginate chains are restricted by the chemical PAAm network and undergo a confined-chain aggregation, which guarantees an interpenetrating network of both polymers and simultaneously generates micron-scale aggregates. In addition, after the subsequent water uptake, the accompanying formation of hydrogen bonds and metal-ligand coordination stabilizes the newly formed alginate aggregates, serving as large-scale cross-linking zones. However, the PAAm chains are anchored by the preformed cross-linking points and convert back to the uniformly distributed, high-water-content state, achieving a selected phase separation in a DN system. The combined CCA and hybrid cation cross-linking method gives mechanical strength and toughness to the PAAm/Alg hydrogels to reach approximately 30 and 5 times the traditional methods, respectively. This investigation provides a general strategy for the development of a new generation of double-network hydrogels, which will expand their application as structural materials for cartilage and soft robotics.