Abstract
We report the discovery of a new nanostructured morphology in ultrathin blend films of semi-crystalline poly(ε-caprolactone) (PCL) and various styrene-isoprene block copolymers. The nano-rose morphology is visualized by atomic force microscopy as a monolayer of approximately 500 nm diameter crystalline spirals. Our finding that the nano-rose morphology occurs in a narrow film thickness window commensurate with the crystalline lamellar thickness suggests that this distinctive morphology results from redirection of growing PCL crystalline lamellae due to confinement effects during film casting. The nano-rose morphology was located in blends with several block copolymers of various architecture but was absent in blends with the individual homopolymer components. PCL molecular weight did not affect nano-rose size or film thickness window. However, solvent choice was an important factor, with nano-rose formation favored in non-polar and weakly polar solvents. This work supports theories that unbalanced surface stresses and impurity exclusion cause polymer crystals to grow unconventionally.
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