Strain Softening of Styrene-Isoprene-Styrene Copolymers under Large Amplitude Oscillatory Shear for Clarifying Payne Effect in Rubbers and Their Nanocomposites

To illustrate mechanisms of Payne effect in rubbers and their nanocomposites experiencing large amplitude oscillatory shear(LAOS),comparison studies were performed in styrene-isoprene-styrene(SIS)copolymers and their selectively crosslinked materials at temperatures below and above glass transition temperature of the polystyrene(PS)phase.It was found that under periodic dynamic shear,the strain softening is reversible when the polyisoprene(PI)phase,either crosslinked or not,is restricted by hard PS domains but it shows hysteresis once the PS domains disassociate.The strain softening can happen at the time scale of intrinsic Rouse relaxation of elastically active network strands.Critical stress of strain softening scales with number density of elastically active network strands,a simple relation being verified not only in the selectively crosslinked SIS copolymers but also in PI gum vulcanizates and carbon black filled PI compounds.Payne effect is traditionally used to term strain softening of highly filled rubber vulcanizates under LAOS deformation while evidenced herein is that the Payne effect of highly filled rubber vulcanizates shares the mechanism being common to the strain softening of SIS copolymers.

Large Amplitude Oscillatory Shear Studies on the Strain-stiffening Behavior of Gelatin Gels

Linear and nonlinear viscoelasticity of gelatin solutions was investigated by rheology. The dynamic mechanical properties during the sol-gel transition of gelatin followed the time-cure superposition. The fractal dimension df of the critical gel was estimated as 1.76, which indicated a loose network. A high sol fraction ws = 0.61 was evaluated from the plateau modulus by semi-empirical models. Strain-stiffening behavior was observed under large amplitude oscillatory shear（LAOS） for the gelatin gel. The strain and frequency dependence of the minimum strain modulus GM, energy dissipation Ed, and nonlinear viscoelastic parameter NE was illustrated in Pipkin diagrams and explained by the strain induced helix formation reported previously by others. The BST model described the strain-stiffening behavior of gelatin gel quite well, whereas the Gent and worm-like chain network models overestimated the strain-stiffening at large strains.