title: Branched Crystalline Patterns of Poly(ε-caprolactone) and Poly(4-hydroxystyrene) Blends Thin Films.
abstract: The chain organization of poly(ε-caprolactone) (PCL) in its blend with poly(4-hydroxystyrene) (PVPh) in thin films (130 ± 10 nm) has been revealed by grazing incident infrared (GIIR) spectroscopy. It can be found that PCL chains orient preferentially in the surface-normal direction and crystallization occurs simultaneously. The morphology of the PCL/PVPh blends films can be identified by optical microscopy (OM). When crystallized at 35 °C, the blends film shows a seaweed-like structure and becomes more open with increasing PVPh content. In contrast, when crystallized at higher temperatures, i.e., 40 and 45 °C, dendrites with apparent crystallographically favored branches can be observed. This characteristic morphology indicates that the diffusion-limited aggregation (DLA) process controls the crystal growth in the blends films. The detailed lamellar structure can be revealed by the height images of atomic force microscopy (AFM), i.e., the crystalline branches are composed of overlayered flat-on lamellae. The branch width has been found to be dependent on the supercooling and PVPh content. This result differs greatly from pure PCL, in which case the crystal patterns controlled by DLA process developed in ultrathin film or monolayers of several nanometers. In the PCL/PVPh blends case, the strong intermolecular interactions and the dilution effect of PVPh should contribute to these results. That is to say, the mobility of PCL chains can be retarded and diffusion of them to the crystal growth front slows down greatly, even though the film thickness is far more than the lamellar thickness of PCL.
authors.affiliation: State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Beijing 100029, China.
authors.forename: Chunyue
authors.initials: C
authors.lastname: Hou
authors.affiliation: State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Beijing 100029, China.
authors.forename: Tianbo
authors.initials: T
authors.lastname: Yang
authors.affiliation: State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Beijing 100029, China.
authors.forename: Xiaoli
authors.initials: X
authors.lastname: Sun
authors.affiliation: State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Beijing 100029, China.
authors.forename: Zhongjie
authors.initials: Z
authors.lastname: Ren
authors.affiliation: State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Beijing 100029, China.
authors.forename: Huihui
authors.initials: H
authors.lastname: Li
authors.affiliation: State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology , Beijing 100029, China.
authors.forename: Shouke
authors.initials: S
authors.lastname: Yan