SAOS and LAOS rheology for differentiating chemical and physical crosslinking: A case study on PVA hydrogels
David Kogan, Moshe Gottlieb
Abstract
Abstract In this work, we have studied the viscoelastic behavior of chemically and physically crosslinked Poly(vinyl alcohol) (PVA) hydrogels near the critical gel point (GP) as well as further away from it, by means of small amplitude (SAOS) and large amplitude (LAOS) oscillatory shear experiments. Chemical crosslinking involved covalent bonding by means of glutaraldehyde as a crosslinker, while physical crosslinking was induced by freeze–thaw cycles. SAOS data analysis allowed evaluation of critical parameters such as the critical relaxation exponent n , gel strength S , and equilibrium modulus Ge , based on the dynamic self-similarity and fractal network structures at the GP. LAOS rheological data analysis showed that the chemically crosslinked system exhibited moderate strain-dependance due to the permanent covalent bonds, whereas the physically crosslinked system displayed significant strain-dependent nonlinearity due to strain dependent interactions at the crosslink entities. LAOS experiments, supported by Chebyshev coefficients and Lissajous-Bowditch plots, highlighted pronounced differences in nonlinear responses, underscoring the influence of crosslinking mechanisms on the network rheological behavior. The findings establish LAOS as a powerful tool for differentiating polymeric network structures, providing insights beyond those attained by conventional linear rheology.