A series of semi-crystalline block copolymers, poly(4-vinylpyridine)-b-poly(ε-caprolactone) (P4VP-PCL), have been synthesized. Different crystallization processes were carried out for the growth of single crystals. For comparison, PCL homopolymers were also synthesized for crystallization. Typical lamellar single crystals of the PCL homopolymers crystallized from melt could be observed at which the crystalline lamellae appear as truncated lozenge shape under transmission electron microscopy (TEM) observation and flat-on morphology (the molecular chains are perpendicular to the basal plane of the lamellae) can be found as evidenced by the selective area electron diffraction (SAED). By contrast, irregular shape of crystalline lamellae was observed for the melt-crystallized P4VP-PCL, suggesting that the amorphous P4VP segment may perturb the growth of lamellar single crystals for the melt crystallization of P4VP-PCL. Note that there is also significant effect from the dense nucleation for melt-crystallized P4VP-PCL. To well develop the lamellar growth, solution crystallization was conducted. The lamellar single crystals of PCL growing from a dilute solution of n-hexanol appeared as well-defined PCL single crystals with clear sectors. Interestingly, the lenticular-shaped lamellar single crystals of the P4VP-PCL growing from a dilute solution of n-hexanol can be obtained. The solution-crystallized lamellar crystals also appeared as flat-on morphology. Furthermore, the lamellar crystals were grown as serrated shape in the edge. Also, by varying the solvent system for solution crystallization, a specific fractal texture for the grown lamellae can be found. As a result, our results suggest that various single-crystalline textures from the semi-crystalline P4VP-PCL can be obtained by adjusting the crystallization condition for growth. Most importantly, on the basis of the morphological observations, we speculate that the amorphous P4VP chains are regularly distributed on the fold surface of the PCL single crystals. Moreover, the P4VP brushes on the PCL lamellae could be formed as fingerprint, nodule and layer-like textures by justifying the crystallization condition from solution. A specific crystallization behavior of the block copolymers was found at which micelle-like texture could be formed in the solution from P4VP-PCL microphase separation and followed by the PCL crystallization to lead the formation of single crystal morphology with P4VP nodules on the lamellar surface.
By taking advantage of various textures for P4VP brushes on the PCL lamellae, we aim to use the variety of lamellar textures as templates for the decoration of functional inorganic nanoparticles through their association with the P4VP. We predict that patterning of functional inorganic nanoparticles could be achieved by incubating these single crystals with inorganic nanoparticles on the P4VP brushes and the inorganic nanoparticles areal density could be easily controlled by PCL molecular weight as well as the decorative quantity by controlling molecular weight of P4VP blocks.

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