Finite size effects in multilayered polymer systems: Development of PET lamellae under physical confinement

The glass transition temperature and the crystallization behaviour of poly(ethylene terephthalate) PET ultra-thin layers (a few tens of nm) within multilayered PET/polycarbonate (PC) coextruded films are investigated as a function of layer thickness by means of calorimetric measurements. Results are discussed in terms of reduced thickness and interface effects. The appearance and evolution of lamellar orientation upon isothermal crystallization of ultra-thin PET layers from the glassy state are explored based on real time small-angle X-ray scattering (SAXS) studies. Analysis of the SAXS measurements reveals that finite size effects hamper the crystallization process. However, the final lamellar structure is similar in both, the nanolayered PET and the bulk material. Results suggest that not only lamellar insertion but also some lamellar thickening contribute to the development of the final lamellar structure. Room temperature SAXS and wide-angle X-ray diffraction (WAXS) measurements indicate that two lamellar populations develop: edge-on lamellae are proposed to appear close to the interphases while flat-on lamellae, arising as a consequence of confinement, should be preferentially located in the layers core.