title: Crystallization of Polymer Chains Chemically Attached on a Surface: Lamellar Orientation from Flat-on to Edge-on.
abstract: Crystallization of polymer chains confined on a surface greatly influences surface properties. We have grafted comb-like copolymer, consisting of poly(2-hydroxyethyl methacrylate) (PHEMA) backbone and semicrystalline poly(ε-caprolactone) (PCL) side chains, on silicon surface and investigated the crystallization of such confined PCL chains upon solvent evaporation by using atomic force microscopy (AFM), grazing incidence wide-angle X-ray scattering (GI-WAXS), and polarized optical microscope (POM). Our studies reveal that the PCL chains align and form "flat-on" lamellae at a low PCL chain density. As the chain density increases, the comb-like polymer (PHEMA-g-PCL) chains undergo pancake-to-mushroom-to-brush transition, and the lamellae turn from "flat-on" to "edge-on" in orientation. Further increasing PCL chain density leads the "edge-on" lamellae to change from a quasi-two-dimensional (quasi-2D) to quasi-three-dimensional (quasi-3D). Because of the confinements of polymer chains, we can observe the evolution of spherulites at different stages during the mushroom-to-brush transition of PHEMA-g-PCL chains. The confinements also result in knobbly substructures in the edge-on lamellae.
authors.affiliation: Faculty of Materials Science and Engineering, South China University of Technology , Guangzhou 510640, P. R. China.
authors.forename: Yihuang
authors.initials: Y
authors.lastname: Chen
authors.affiliation: Faculty of Materials Science and Engineering, South China University of Technology , Guangzhou 510640, P. R. China.
authors.forename: Tiansheng
authors.initials: T
authors.lastname: Gan
authors.affiliation: Faculty of Materials Science and Engineering, South China University of Technology , Guangzhou 510640, P. R. China.
authors.forename: Chunfeng
authors.initials: C
authors.lastname: Ma
authors.affiliation: Faculty of Materials Science and Engineering, South China University of Technology , Guangzhou 510640, P. R. China.
authors.forename: Linge
authors.initials: L
authors.lastname: Wang
authors.affiliation: Faculty of Materials Science and Engineering, South China University of Technology , Guangzhou 510640, P. R. China.
authors.forename: Guangzhao
authors.initials: G
authors.lastname: Zhang