Crystalline morphology evolution in PCL thin films

The transition of crystalline morphology is revealed in poly(E-caprolactone) (PCL) thin films as the polymer film thickness changes from hundreds of nanometers to several nanometers. The PCL can crystallize into spherulites, densebranching morphology (DBM), or dendrites, depending on the polymer film thickness. It was found that when the polymer film thickness approaches 2Rg (radius of gyration of polymer), there is a remarkable change in crystalline morphology. Under this condition, the polymer crystallization is a diffusion-controlled process. When the value of polymer film thickness closes to Rg, PCL cannot crystallize, and a dewetting phenomenon will take place. Moreover, polymer morphology can be controlled by varying supercooling. The effect of molecular weight on polymer morphology has been investigated. The main factors that affected pattern formation in nonequilibrium crystallization are also discussed. (c) 2005 Wiley Periodicals, Inc.