A series of semicrystalline block copolymers, poly(4-vinylpyridine)-block-poly(ε-caprolactone)
(P4VP−PCL), with lamellar microstructure have been synthesized. Owing to the vitrified P4VP microdomains
and strongly segregated microphase separation, the crystallization of the PCL blocks in P4VP−PCL was carried
out within the nanoscale confinement. Simply by varying the molecular weight of the block copolymer, namely
the confined size, polymeric crystallization can be tailored in the one-dimensional confinement. A distinct nucleation
mechanism, altering from heterogeneous to homogeneous nucleation, was obtained once the confined size became
smaller than a critical dimension, equivalent to the regular thickness of heterogeneously nucleated crystalline
lamellae. Consequently, discrete crystalline granules were generated through homogeneous nucleation, namely a
single nucleus within one granule. Also, crystal growth was altered from specific to random orientation with
respect to the interface between the crystalline and amorphous domains in the copolymers. This system thus
serves as a model to analyze the impact of confined size in 1D spatial confinement on the crystallization of
polymers.
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