Solvent-induced aggregation of regioregular head-to-tail poly(3-alkylthiophene)s (PATs) have been studied by means of AFM and UV−vis spectroscopy. In hexane, which is a good solvent for alkyl side chains but poor for polythiophene backbones, PAT molecules undergo ordered main-chain collapse driven by solvophobic interaction. Well-pronounced concentration-independent red shift of λ max and good resolved fine vibronic structure in the electronic absorption spectra observed upon addition of hexane indicate that planarization occurs on the singlemolecule level. A helical conformation of the man chain of PATs with 12 thiophene rings per each helical turn has been proposed. At the higher concentration of PATs the collapsed molecules undergo unexpected one-dimensional aggregation. Length of the particles varies from several nanometers to several hundreds nanometers and can be easily adjusted by the solvent composition or concentration of PATs.

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The crystallization and nucleation kinetics of poly(ε-caprolactones) (PCL) with molar masses between 1.4 and 6.1 kDa and negligible number of heterogeneous nuclei has been investigated by differential fast scanning calorimetry (DFSC) applying scanning rates up to 100 000 K/s. The samples were synthesized by ring-opening polymerization and chemically characterized by NMR spectroscopy, size exclusion chromatography (SEC), and multiangle laser light scattering (MALLS). For the smallest molar mass the chain length is comparable with the crystal thickness measured with small-angle X-ray scattering (SAXS), and extended chain like crystals may be formed. Because of the molar mass distribution (PDI ≈ 2), these crystals have a significant noncrystalline interface yielding nearly the same crystallinity for all molar masses. The critical cooling rate to obtain amorphous samples is below 1000 K/s and only for the lowest molar mass increased to 2000 K/s. The same trend holds for the about 1 order of magnitude higher critical heating rate to keep the samples amorphous on heating and for the analysis of isothermal nucleation and crystallization kinetics at 202 K. The samples which were shown not to contain heterogeneous nuclei active at a heating rate of >18 000 K/s were used for a study of the nucleation activity of ordered structures formed on annealing at low temperature. The analysis of the change of the thus-produced amorphous polymer samples on annealing from 202 to 272 K for times varying by a factor of more than 108 (0.1 ms to 8.3 h) revealed new details about the ordering processes (nucleation, poor crystal formation, crystallization, cold crystallization, and crystal perfection) and the accompanying changes in glass transition of the remaining amorphous phase (formation of rigid amorphous phases, RAF).

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