Abstract
AbstractSingle‐chain single crystals of isotactic polystyrene and poly(ethylene oxide) were studied by using transmission electron microscopy, high resolution electron microscopy, electron diffraction. Single‐chain single crystals were prepared by spreading a dilute solution of polymers on a water surface and collecting the resulting single‐chain particles on copper grids, followed by isothermal crystallization. A statistical analysis of the sizes of single‐chain crystals was found to match with the known molecular weight distribution of original sample, indicating the particles to be composed of single chain. Observation of the morphology and electron diffraction gave evidence of the single crystal nature. Regular‐shaped single‐chain crystals were obtained after isothermal crystallization for a longer time. By close observation, several types of morphologies were found for single‐chain crystals of isotactic polystyrene and poly(ethylene oxide); in addition to the conventional morphologies observed for multi‐chain crystals, new morphologies were observed in both cases. The morphologies of poly(ethylene oxide) were explained according to the crystal structure and twin modes. Tent‐like single‐chain crystals were often observed. Because of the small size of the crystals, they can avoid collapse on the substrate. The crystalline c‐axis of single‐chain crystals were found to orient preferably in the direction normal to the substrate. The investigation of electron diffraction and high resolution electron microscopy revealed that the structure of the single‐chain crystals of isotactic polystyrene is the same as for multi‐chain crystals. A reasonable explanation is given for the unusual resistance to electron irradiation and the missing of lower‐index reflections. Regular periodic stripes were found on the top surface of single‐chain crystal of isotactic polystyrene with an average periodic length in accordance with (220) spacing. In addition, a statistical thermodynamics theory was developed for single‐chain crystal. It is found that the equilibrium dimensions are related to molecular weight and annealing temperature, while the equilibrium melting temperature depends on molecular weight.
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