Hydrogel Films with Impact Resistance by Sacrificial Micelle‐Assisted‐Alignment

Abstract Various strategies are developed to engineer aligned hierarchical architectures in polymer hydrogels for enhanced mechanical performance. However, chain alignment remains impeded by the presence of hydrogen bonds between adjacent chains. Herein, a facile sacrificial micelle‐assisted‐alignment strategy is proposed, leading to well‐aligned, strong and tough pure chitosan hydrogels. The sacrificial sodium dodecyl sulfate micelles electrostatically interact with the protonated chitosan chains, enabling chain sliding and alignment under uniaxial forces. Subsequently, sacrificial micelles can be easily removed via NaOH treatment, causing the reforming of H‐bond in the chain networks. The strength of the pure chitosan hydrogels increases 140‐fold, reaching 58.9 ± 3.4 MPa; the modulus increases 595‐fold, reaching 226.4 ± 42.8 MPa. After drying‐rehydration, the strength and modulus further rise to 70.3 ± 2.4 and 403.5 ± 76.3 MPa, marking a significant advancement in high‐strength pure chitosan hydrogel films. Furthermore, the designed multiscale architectures involving enhanced crystallinity, well‐aligned fibers, strong interfaces, robust multilayer Bouligand assembly contribute to the exact replica of lobster underbelly with impact resistance up to 6.8 ± 1.0 kJ m −1 . This work presents a promising strategy for strong, tough, stiff and impact‐resistant polymer hydrogels via well‐aligned hierarchical design.