Confined/Unconfined Crystallization of Poly(۳-Hexylthiophene) in Melt/Solution Environments Containing Carbonic Materials and Correlated Thermal and Structural Behaviors

Confined and unconfined crystallizations of poly(۳-hexylthiophene) (P۳HT) were studied in the solution-grown supramolecules and melt-grown systems using a differential scanning calorimeter. The carbon nanotube (CNT) and reduced graphene oxide (rGO) and their functionalized (CNT-f-COOTh and rGO-f-TAA) and grafted (CNT-g-PDDT and rGO-g-PDDT) derivatives were employed to develop the samples. The absorbance, structure details via Scherrer formula, fusion enthalpy (ΔHm) and crystallinity (Xc) were measured in two distinct confined/unconfined crystallization environments. Although the functionalized-CNT/rGO precursors partially reduced the crystallite qualities with respect to the pristine CNT and rGO ones in the solution-grown supramolecules, they did not affect the structural properties in the melt-grown samples. Grafted carbonic materials could be considered as appropriate seeds for the arrangement of P۳HTs in both solution and melt crystallizations. The best absorbances, larger and more compact crystals, and higher melting point, ΔHm, and Xc values were recorded for the pre-developed CNT-g-PDDT/P۳HT stem-leaf (۶.۰۹–۲۲.۵۱ nm, ۳.۵۲–۱۳.۸۹ Å, ۲۳۹.۸ °C, ۳۰.۸۶ J/g and ۸۳.۴۰%) and rGO-g-PDDT/P۳HT coarse-patched (۵.۹۶–۲۰.۷۶ nm, ۳.۵۷–۱۳.۹۵ Å, ۲۳۷.۶ °C, ۲۹.۱۳ J/g and ۷۸.۷۳%) supramolecules. Although the melt-grown CNT-g-PDDT/P۳HT (۲۰۱.۴ °C, ۲۱۵.۳ °C, ۱۶.۲۲ J/g and ۴۳.۸۴%) and rGO-g-PDDT/P۳HT (۲۰۵.۴ °C, ۲۱۸.۸ °C, ۱۸.۰۶ J/g and ۴۸.۸۱%) nanostructures were not as perfect as the respective solution-grown nano-hybrids, they were well-arranged with respect to the CNT/P۳HT, CNT-f-COOTh/P۳HT, rGO/P۳HT and rGO-f-TAA/P۳HT samples

Keywords:

Crystallization , P۳HT , supramolecule , Scherrer formula , fusion enthalpy