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Understanding and controlling the morphology of thermoplastic polyurethane (TPU) is crucial, as it is closely linked with its thermal and mechanical properties. The morphology of a TPU with a high hard segment content was investigated. When hard segment crystallisation was avoided by fast cooling, a crystallisation-induced phase separation occurred upon reheating. At higher temperatures, a second polymorph was additionally created. Cooling slowly from the melt directly induced the formation of both polymorphic forms. The complex thermal behaviour could hence be explained by the (cold) crystallisation and melting of two polymorphs. The disordered two-phase nanomorphology, revealed by AFM at room temperature after cooling slowly, was validated for both fast and slowly cooled samples at higher temperatures by fitting model SAXS patterns to time resolved synchrotron SAXS data. Annealing fast cooled samples at high temperature induced some ordered, lamellar stacks in addition. Finally, the morphology was linked to the evolution of storage modulus with increasing temperature.

End-group-functionalized hyperbranched polymers were synthesized to act as a carbon nanotube (CNT) surfactant in aqueous solutions. Variation of the percentage of triphenylmethyl (trityl) functionalization and of the molar mass of the hyperbranched polyglycerol (PG) core resulted in the highest measured surfactant efficiency for a 5000 g/ mol PG with 5.6% of the available hydroxyl end-groups replaced by trityl functions, as shown by UV−vis measurements. Semiempirical model calculations suggest an even higher efficiency for PG5000 with 2.5% functionalization and maximal molecule specific efficiency in general at low degrees of functionalization. Addition of trityl groups increases the surfactant−nanotube interactions in comparison to unfunctionalized PG because of π−π stacking interactions. However, at higher functionalization degrees mutual interactions between trityl groups come into play, decreasing the surfactant efficiency, while lack of water solubility becomes an issue at very high functionalization degrees. Low molar mass surfactants are less efficient compared to higher molar mass species most likely because the higher bulkiness of the latter allows for a better CNT separation and stabilization. The most efficient surfactant studied allowed dispersing 2.85 mg of CNT in 20 mL with as little as 1 mg of surfactant. These dispersions, remaining stable for at least 2 months, were mainly composed of individual CNTs as revealed by electron microscopy.