Institute of Chemistry, The Chinese Academy of Science, Beijing 100190, PR China.
J Phys Chem B. 2010 Oct 21;114(41):13104-9. doi: 10.1021/jp106995f.
It is confirmed that a layer of vacuum-evaporated carbon on the surface of a preoriented ultrathin polymer film can lead to an oriented recrystallization of the polymer film. This has been attributed to a strong fixing effect of vacuum-evaporated carbon layer on the film surface of the polymer. To study the origin of the strong fixing effect of vacuum-evaporated carbon layer on the polymer films, the melting and recrystallization behaviors of the preoriented ultrathin PE film with a vacuum-evaporated carbon layer were studied by using atomic force microscopy, electron diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. We found that there exists some extent of chain orientation of carbon-coated polyethylene (PE) preoriented ultrathin film above its melting temperature. These oriented PE chain sequences act as nucleation sites and induce the oriented recrystallization of preoriented PE film from melt. Raman spectroscopy results suggest that new carbon-carbon bonds between the carbon layer and the oriented PE film are created during the process of vacuum carbon evaporation. As a result, some of the PE chain stems are fixed to the coated carbon substrate via covalent bond. Such a bonding has retarded the relaxation of the PE chains at the spot and, therefore, preserves the original orientation of the PE stems at high temperature, which in turn derives the recrystallization of the PE chains in an oriented structure.
经证实,在取向的超薄膜聚合物表面蒸镀一层真空碳可以导致聚合物膜的取向再结晶。这归因于真空碳层对聚合物膜表面的强烈固定作用。为了研究真空碳层对聚合物膜的强烈固定作用的起源,使用原子力显微镜、电子衍射、傅里叶变换红外光谱和拉曼光谱研究了具有真空碳层的预取向超薄 PE 膜的熔融和再结晶行为。我们发现,在其熔点以上,涂覆碳的聚乙烯(PE)预取向超薄膜存在一定程度的链取向。这些取向的 PE 链序列充当成核位点,并诱导预取向 PE 膜从熔体中取向再结晶。拉曼光谱结果表明,在真空碳蒸发过程中,碳层与取向 PE 膜之间形成了新的碳-碳键。结果,一些 PE 链主干通过共价键固定在涂覆的碳基底上。这种键合减缓了该点处 PE 链的松弛,因此在高温下保留了 PE 主干的原始取向,从而导致 PE 链以取向结构再结晶。