Molecular orientation in crystalline miscible blends

The orientation induced by stretching uniaxially in the solid state two semi-crystalline miscible blends of poly(epsilon-caprolactone) (PCL) with poly(vinyl chloride) (PVC) and poly(styrene-co-acrylonitrile) (SAN) was investigated by infrared dichroism. In both cases, the deformation of the solution-cast films, having a high PCL crystallinity degree of about 50% and containing up to about 40 wt% of PVC or SAN, leads rapidly to a very high segmental orientation for the crystalline PCL as a result of a structural transformation from lamellae to microfibrils. Meanwhile, the amorphous components, being miscible and located in the interlamellar regions inside the spherulites, show a much lower orientation as compared with the crystalline PCL regardless of the blend composition. SAN is found to orient to the same degree as the amorphous PCL in the PCL/SAN blends, while the orientation of PVC is higher than that of the amorphous PCL in the PCL/PVC blends. Furthermore, the slow crystallization of PCL in blends containing around 40% of PVC made it possible to follow the orientation behaviour as a function of the crystallization time by stretching a series of films before and after the crystallization of PCL started. It was found that, even with as little crystalline PCL as 5% of the total blend weight, the stretching-induced crystalline orientation is almost as high as for the samples with high degrees of crystallinity. A stretching-induced crystallization forming microfibril-like crystallites of PCL is suggested to be at the origin of the high crystalline orientation for those blends, which have a dominant proportion of amorphous components during the stretching, instead of the transformation of existing lamellae to the microfibrillar structure for stretched highly crystalline blends. (C) 1998 Elsevier Science Ltd. All rights reserved.