Linear Dynamic Viscoelasticity of Dual Cross-Link Poly(Vinyl Alcohol) Hydrogel with Determined Borate Ion...

We investigated the linear dynamic viscoelasticity of dual cross-link (DC) poly(vinyl alcohol) (PVA) (DC-PVA) hydrogels with permanent and transient cross-links. The concentrations of incorporated borate ions to form transient cross-links in the DC-PVA hydrogels (C_B^IN) were determined by the azomethine-H method. The dynamic viscoelasticity of the DC-PVA hydrogel cannot be described by a simple sum of the dynamic viscoelasticity of the PVA gel with the same permanent cross-link concentration and the PVA aqueous solution with the same borate ion concentration (C_B = C_B^IN) as in the DC-PVA gel. The DC-PVA hydrogel exhibited a considerably higher relaxation strength, indicating that the introduction of permanent cross-links into temporary networks increases the number of viscoelastic chains with finite relaxation times. In contrast, the relaxation frequency (ω_c) (given by the frequency at the maximum of loss modulus) for the DC-PVA hydrogel was slightly lower but comparable to that for a dilute PVA solution with the same C_B. This signifies that the relaxation dynamics of the DC-PVA hydrogels is essentially governed by the lifetime of an interchain transient cross-link (di-diol complex of boron). The effect of permanent cross-linking on the relaxation dynamics was observed in the finite broadening of the relaxation-time distribution in the long time region.