Sculpting Mechanical Properties of Hydrogels by Patterning Seamlessly Interlocked Stiff Skeleton

Abstract Functional soft materials, especially hydrogels have been widely developed to achieve various soft structures and machines. However, synthetic hydrogels commonly show formula‐dependent mechanical properties to fulfill the requirements of mechanical elasticity, stiffness, toughness, and tearing‐resistance for adapting to complex application scenario. Inspired by heterostructures and materials found in nature such as leaves and insect wings, a sequential photopolymerization process combined with site‐selective patterning exposure is reported to prepare programmable hydrogels with locally heterogeneous reinforcement skeletons, i.e., interpenetrating double networks. The heterogeneous interface between soft matrices and stiff skeletons is seamlessly interlocked through strong multiple hydrogen bonds induced by phase transition. By harnessing the size, shape, and distribution of the patterned stiff skeletons, a wide range of mechanical properties of hydrogels including modulus (0.32–5.92 MPa), toughness (0.15–18 kJ m −2 ), dissipated energy (1–100 kJ m −3 ), impact resistance, and mechanical anisotropy can be readily sculpted within one material system without needing design and optimization of the complex and elusive material formulation on demand. It is believed that this simple yet powerful method relying on heterogenous patterning would guide the development of functional hydrogel materials with programmable mechanical properties toward potential engineering applications, such as damping and flexible circuits.