From Nano-Crystals to Periodically Aggregated Assembly in Arylate Polyesters—Continuous Helicoid or Discrete Cross-Hatch Grating?

This work used several model arylate polymers with the number of methylene segment n = 3, 9, 10, and 12, which all crystallized to display similar types of periodically banded spherulites at various T(c) and kinetic factors. Universal mechanisms of nano- to microscale crystal-by-crystal self-assembly to final periodic aggregates showing alternate birefringence rings were probed via 3D dissection. The fractured interiors of the birefringent-banded poly(decamethylene terephthalate) (PDT) spherulites at T(c) = 90 °C revealed multi-shell spheroid bands composed of perpendicularly intersecting lamellae bundles, where each shell (measuring 4 μm) was composed of the interior tangential and radial lamellae, as revealed in the SEM results, and its shell thickness was equal to the optical inter-band spacing (4 μm). The radial-oriented lamellae were at a roughly 90° angle perpendicularly intersecting with the tangential ones; therefore, the top-surface valley band region appeared to be a submerged “U-shape”, where the interior radial lamellae were located directly underneath. Furthermore, the universal self-assembly was proved by collective analyses on the three arylate polymers.