The dual effects of non-solvent on the sol-gel transition of polyacrylonitrile solution: The promotion in thermodynamics and hindrance in kinetics

Abstract

The effects of non-solvent on the sol-gel transition of polyacrylonitrile (PAN) solution were investigated in thermodynamics and kinetics by the means of rheology method. The facilitating effects of non-solvent in thermodynamics was illustrated by the variety of viscoelasticity and gel transition temperature (Tgel). With the addition of non-solvent, the mobility of PAN molecular chains are limited due to its increased entanglement. As a result, the PAN solution with higher non-solvent content has lower conformation entropy to satisfy the occurrence of sol-gel transition at higher temperature. It means that less thermodynamic driving is demanded. The kinetical characteristics of PAN solution with different non-solvent content in sol-gel transition process were also discussed. The kinetic hindrance of non-solvent was proved by the gradually stronger time-dependence of loss tangent with the addition of non-solvent during sol-gel transition. This apparent extending of relaxation time is resulted from the more restriction of the mobility of PAN molecules. The gelation activation energy (Egel) was calculated according to Ozawa method. The results also indicated that the activity of PAN molecules in this transition became weaken with the addition of non-solvent since a relative tight connection between PAN molecules was there. Therefore, the formation of physical junction points for sol-gel transition was hindered due to the decreasing of the mobility of self-adjustment for PAN molecules. This is the fundamental reason for the kinetic hindrance role of non-solvent.