Iridescent Features Correlating with Periodic Assemblies in Custom-Crystallized Arylate Polyesters.

In this study, five different aryl polyesters, i.e., poly(ethylene terephthalate) (PET), poly(trimethylene terephthalate) (PTT), poly(octamethylene terephthalate) (POT), poly(nonamethylene terephthalate) (PNT), and poly(decamethylene terephthalate) (PDT), upon crystallization at a suitable temperature range, all exhibit ring-banded spherulites with universal characteristics. Previous research has revealed some fundamental mechanisms underlying the formation of periodic hierarchical structures. Additionally, this study further explored correlations among micro/nanocrystal assemblies in the top surface and internal grating architectures and the structural iridescent properties. The interior lamellar assembly of arylate polyesters' banded spherulites is shown to exhibit periodic birefringence patterns that are highly reminiscent of those found in a variety of biological structures, with the capacity for iridescence from light interference. A laser diffraction analysis was also used to support confirmation of this condition, which could result in an arc diffraction pattern indicative of the presence of ringed spherulites. Among the five arylate polyesters, only PET is incapable of regularly producing ring-banded morphology, and thus cannot produce any iridescent color.

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 Tc 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 Tc = 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.