Hydrogels engineered with specific surface chemistries and architectures have found myriad applications in electronics, biofouling, biolubrication, and biomedical devices. Free-radical polymerization is frequently employed to construct covalently bonded networks in hydrogels, and any inhibition of the radical reactions by oxygen at the surface of the reaction mixture is generally undesirable. The internal stress caused by the resulting gradient in the cross-linking density during polymerization can give rise to a physical deformation of the surface, resulting in wrinkles, creases, or cracks. However, this oxygen-inhibition effect can be positively utilized to create finely controlled surface structures. We describe a two-step cross-linking strategy for the fabrication of a P(AAm-AMPS)/alginate double-network hydrogel in the presence of air, which enables greater independent control over surface chemistry and functionality than homogeneously processed conventional double-network hydrogels. An alginate-rich "skin" layer is spontaneously delaminated due to the mechanical instability and osmotic mismatch between the swollen double-network hydrogel matrix and the rigid "skin" layer. Removal of the "skin" layer results in a lubricious surface with coefficients of friction as low as 0.02 against glass in aqueous solutions. The proposed strategy can be generalized to develop soft functional materials with unique structures and properties and precise control over the surface chemistry.
Keywords: cross-linking gradients; delamination; hydrogels; lubricious surfaces; oxygen inhibition.