화학공학소재연구정보센터
Journal of Applied Polymer Science, Vol.57, No.9, 1095-1103, 1995
Thermodynamical Approach to Polymer Rheology
The model of pseudocrosslink is extended to polymer rheology. There exist various sizes b of 4-16 between transition points A and B. Each link is connected with a chain having length nb and relaxation time tau(b). n(b) is equal to b(2) and tau(b) is proportional to n(b)(2). A, B, and C (polymer terminal) divide the stress-relaxation spectrum into four zones. In the AB zone, successive dissociation of links occurs from a small size to a large one and rigidity G is decreased with time t as G proportional to t(-0.5) and viscosity eta is increased as G proportional to t(0.5). In the BC zone, dissociation of the B link proceeds along a molecule of length n in a mode of squeezing of molecule and eta becomes constant, but G still decreases due to increase of unperturbed end-to-end distance of chain and G proportional to t(-0.5). However, dynamic elasticity becomes constant due to a small amplitude. At high shear, links are loosened and C and eta are much decreased. Beyond C, molecule flows and eta increases as eta proportional to gamma(-0.8) n(3.5), but high shear rate gamma diminishes the effect of n due to extension of the molecule. Extensional viscosity eta* is affected by the change of shape as eta* proportional to t(1.5) and gives an overshoot. Under load, creep occurs and it is proportional to t(1/2-1/3).