Peculiar Poly(ε-caprolactone) Periodic-Dendritic Aggregates: Architecture and Assembly Mechanism Probed Using X-ray Microbeam

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High Resolution Image Download MS PowerPoint Slide This study explores the temperature-dependent crystallization and morphology of poly(ε-caprolactone) (PCL) blended with poly(phenyl methacrylate) (PPhMA) in an 80/20 ratio, revealing distinct spherulitic structures. At lower temperatures, ring-banded spherulites form, transitioning to zigzag-banded spherulites at moderate temperatures and camellia flower-like morphologies at higher temperatures. High-resolution SEM imaging of the flower-like structure highlights densely packed, edge-on lamellae with lobed rims, forming a dome-shaped surface, while the zigzag spherulites exhibit dendritic, periodic growth from the nucleus, with lamellae shifting from flat-on to edge-on orientations. SAXS microbeam analysis confirms stable crystallinity across structures, with broader lamellar spacing in ridges than in valleys, highlighting anisotropic internal organization. Microbeam X-ray diffraction mapping reveals a complex assembly of edge-on lamellae in ridges and flat-on lamellae in valleys, forming a grating-like pattern in ring-banded spherulites. These findings underscore the intricate temperature-sensitive self-assembly and local compositional variations within PCL/PPhMA blends, enhancing our understanding of hierarchical organization in polymer blends.

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