화학공학소재연구정보센터
Rheologica Acta, Vol.53, No.9, 725-739, 2014
Experimental study on the capillary thinning of entangled polymer solutions
The transient elongation behavior of entangled polymer and wormlike micelles (WLM) solutions has been investigated using capillary breakup extensional rheometry (CaBER). The transient force ratio X = 0.713 reveals the existence of an intermediate Newtonian thinning region for polystyrene and WLM solutions prior to the viscoelastic thinning. The exponential decay of X(t) in the first period of thinning defines an elongational relaxation time lambda (x) which is equal to elongational relaxation time lambda (e) obtained from exponential diameter decay D(t) indicating that the initial stress decay is controlled by the same molecular relaxation process as the strain hardening observed in the terminal regime of filament thinning. Deviations in true and apparent elongational viscosity are discussed in terms of X(t). A minimum Trouton ratio is observed which decreases exponentially with increasing polymer concentration leveling off at Tr-min = 3 for the solutions exhibiting intermediate Newtonian thinning and Tr-min a parts per thousand 10 otherwise. The relaxation time ratio lambda (e)/ lambda (s), where lambda (s) is the terminal shear relaxation time, decreases exponentially with increasing polymer concentration and the data for all investigated solutions collapse onto a master curve irrespective of polymer molecular weight or solvent viscosity when plotted versus the reduced concentration c[ eta], with [ eta] being the intrinsic viscosity. This confirms the strong effect of the nonlinear deformation in CaBER experiments on entangled polymer solutions as suggested earlier. On the other hand, lambda (e) a parts per thousand lambda (s) is found for all WLM solutions clearly indicating that these nonlinear deformations do not affect the capillary thinning process of these living polymer systems.