Multiaxial Stress Relaxation of Dual-Cross-Link Poly(vinyl alcohol) Hydrogels.

Dual-cross-link hydrogels, which are composed of poly(vinyl alcohol) chains cross-linked by covalent bonds and transient physical bonds via borate ions, have received considerable interest due to the high extensibility as well as the self-healing properties. The dual-cross-link gels exhibit pronounced stress relaxation after the imposition of step strain, reflecting the breaking dynamics of temporary chains which sustain the initial stress. Multiaxial stress relaxation experiments using equibiaxial, planar, and uniaxial stretching with various degrees of strain unambiguously validate the time-strain separability in relaxation stress for a general type of deformation. The time effect is satisfactorily described by an existing model, while the strain effect is well approximated by the neo-Hookean model. Furthermore, the magnitude of total stress relaxation to the initial stress is constant, independently of the type and degree of imposed strain. These simple features provide an important basis for formulating the constitutive models of the dual-cross-link gels and for molecular design of hydrogels with transient physical cross-links.