Crystallization behavior of poly(ε-caprolactone) grafted on silicon surface

Abstract

AbstractPoly(ε-caprolactone) (PCL) grafted on silicon wafer with different thickness (10 to 100 nm) were prepared by surface-initiated ring-opening polymerization (ROP). The morphologies, crystallinity, and crystallization rate of different thickness thin films have been investigated by atomic force microscopy (AFM) and Fourier transform infrared spectroscopy (FTIR). The nascent morphology of the as polymerized 15 nm film was found to be nodular structure form. As the film thickness increased, the nodular structures gradually aggregated to form flat-on lamellae. When the film thickness reached 100 nm, the surface of silicon wafer was covered with a whole layer of flat-on lamellae. The isothermal crystallization study on 100 nm film had shown that the tethered PCL chains could only crystallize in the form of flat-on lamellae. FTIR study had showed that the crystallinity decreased significantly with the film thickness decreasing, while the half-crystallization time increased as the film became thicker. The halfcrystallization time increase of thicker film was supposed to relate with the degree of chain entanglement in the tethered brushes.