화학공학소재연구정보센터
Journal of Rheology, Vol.63, No.1, 109-124, 2019
Linear viscoelasticity of weakly cross-linked hydrogels
Chemically cross-linked polyacrylamide (PA) hydrogels have been studied extensively, but gels with a very low cross-linker ratio have received relatively little attention. In this paper, the rheology of bis-cross-linked PA hydrogels is examined with acrylamide concentrations c(a) approximately 10% w/v and cross-linker to acrylamide ratios c(bis)/c(a) in the range 0.2-0.9 mmol mol(-1). Linear viscoelastic responses were measured during and following gelation. The effective cross-link formation rate increases with the cross-linker ratio, with a plateau modulus that is weakly quadratic in the cross-linker ratio. The gels exhibit distinctly different features from their counterparts in the literature with higher cross-linker ratios. Plateau regions in the dynamic moduli spectra are less pronounced, and the loss tangents are several orders of magnitude higher than for gels with a higher cross-linker ratio but a comparable plateau modulus. Time-temperature superposition of viscoelastic spectra furnishes a disentanglement activation energy that decreases with increasing temperature, from approximate to 25 to 6 k(B)T. Time-concentration superposition for samples prepared above the percolation threshold furnishes a critical relaxation exponent Delta approximate to 0.38, which is much smaller than previously reported for the universal sol-gel transition. These distinct features can be attributed to the predominance of entanglements. We show that a Wiechert model with a power-law distribution of relaxation times faithfully reproduces dynamic moduli spectra from the creep compliance. Together, the results provide a foundation with which to interpret acoustic and electroacoustic rheological responses (at MHz frequencies) and the linear viscoelasticity of DNA-cross-linked gels (to be reported elsewhere). (C) 2018 The Society of Rheology.