Mapping hierarchical networks of poly(vinyl alcohol)/cellulose nanofiber composite hydrogels via viscoelastic probes

Discriminating the roles of different networks in the multiply cross-linked hydrogels is vital to optimize their overall performance. Poly(vinyl alcohol)/cellulose nanofiber composite hydrogels were used as template for the study. Three types of characteristic networks, including chemical network cross-linked with boronic ester bonds, physical network cross-linked with microcrystallites, and coexistence of these two networks, were constructed in the system, and the viscoelastic responses were used to detect the characteristic relaxation behavior of those networks. The physical network is more sensitive to stress-induced deformation, whereas the chemical network more sensitive to strain-induced one. The former has lower level of viscous dissipation and higher level of elastic storage as compared to the latter, and dominates linear viscoelasticity of hydrogels as the two networks coexist. Their synergistic effect can be well defined by the scaling behavior of hysteretic work. This work proposes an interesting method of probing networks in the multiply cross-linked hydrogels.