화학공학소재연구정보센터
Rheologica Acta, Vol.35, No.6, 631-644, 1996
Relaxation and viscoelastic properties of complex polymer systems
Dynamic behavior of various polymer melts is studied on the basis of a comparison of viscoelastic properties with the information obtained from dielectric spectroscopy. The experimental observations are compared with results of computer simulation of corresponding systems. The studies include simple melts of linear chains, block copolymer systems of miscible components, as well as the behavior of melts with molecular objects of complex topology-like stars or microgels. In the case of polyisoprene linear chain melts an equivalence of terminal relaxation times determined from mechanical and dielectric measurements is demonstrated. Using linear block copolymers of isoprene and butadiene, relaxation times of chain fragments (isoprene blocks) in relation to relaxation times of whole copolymer chains are determined and compared with theory and simulation. Both the experimentally determined block relaxation times and relaxation times of chain fragments in simulated linear chain melts show a disagreement with predictions of the reptation theory. In the case of multiarm star polymers and microgel melts, the slow relaxation modes observed in viscoelastic spectra are assigned to cooperative translational motions detected in corresponding simulated systems in which an ordering of such molecules is demonstrated. This suggests that the terminal relaxation in multiarm star or microgel melts is governed by another relaxation mechanism than in linear chain melts. High efficiency of the Cooperative Motion Algorithm in simulation of dense systems of complex molecules is demonstrated.