Xingyu Huang, Zhichao Sun, Gen Lu, Zhijun Hu, Lu Chen, Miao Du, Guorong Shan, Qiang Zheng
Hydrogels are promising biomaterials due to their high hydration and biocompatibility. Nevertheless, simultaneously integrating excellent load-bearing capacity and self-lubricating interface into a single hydrogel remains a significant challenging. To address this, we developed a physically cross-linked gradient double-network (GDN) hydrogel based on poly(vinyl alcohol) (PVA) and sodium carboxymethyl cellulose (CMCNa) for biomedical implant applications. The PVA/CMC GDN hydrogel was prepared using a two-step physical cross-linking strategy. First, PVA chains in the mixture formed crystalline domains acting as cross-linking junctions via hydrogen bonding during freezing–thawing cycles, establishing the primary physical network. Subsequently, Al 3+ ions diffused unidirectionally from an Al 2 (SO 4 ) solution into the hydrogel, complexing with CMCNa chains to create a second physical network. The resulting Al 3+ concentration gradient generated a spatially varying cross-linking density, with the bottom region developing a dense double-network structure that endowed the GDN hydrogel with superior load-bearing capacity (macroscopic compressive modulus: 401 kPa). In contrast, the top region retained a single-network structure, ensuring the GDN hydrogel’s excellent self-lubrication. By incorporating the nonionic surfactant Tween 80, the hydrogel achieved an ultralow boundary coefficient of friction reached (9.8 × 10 –3 ) even in the absence of external lubricant. This work not only demonstrates the significant potential of PVA/CMC GDN hydrogels as biomedical implants but also presents a versatile strategy for designing biomimetic architectures with spatially tunable properties.