화학공학소재연구정보센터
Journal of Polymer Science Part B: Polymer Physics, Vol.44, No.20, 3011-3021, 2006
Hole growth as a microrheological probe to measure the viscosity of polymers confined to thin films
We review recent hole growth measurements performed at elevated temperatures in freely-standing polystyrene (PS) films, using optical microscopy and a differential pressure experiment (DPE). In the hole growth experiments, which were performed at temperatures close to the bulk glass-transition temperature of PS, T-g(bulk) = 97 degrees C, we find evidence for nonlinear viscoelastic effects, which markedly affect the growth of holes in freely-standing PS films. The hole radius R initially grew linearly with time t before undergoing a transition to exponential growth characterized by a growth time tau. The time scale tau(1) for the decay of the initial transient behavior prior to reaching steady state was consistent with the convective constraint release mechanism of the tube theory of entangled polymer dynamics, while the characteristic hole growth times tau of the holes were consistent with significant reductions in viscosity of over eight orders of magnitude with increasing shear strain rate due to shear thinning. DPE measurements of hole growth on very thin freely-standing films revealed that hole formation and growth occurs only at temperatures that are comparable to or greater than T-g(bulk) even for films for which the T-g value was reduced by many tens of degrees Celsius below the bulk value. (c) 2006 Wiley Periodicals, Inc.