ZnO Nanorod-Thermoplastic Polyurethane Nanocomposites: Morphology and Shape Memory Performance

The impact of dispersed alkylthiol-modified ZnO nanorods, as a function of rod aspect ratio and concentration, on the shape memory character of a thermoplastic polyurethane with low hard-segment density (LHS-TPU) is examined relative to the enhanced performance occurring for carbon nanofiber (CNF) dispersion. Solution blending resulted in uniform dispersion within the LHS-TPU of the ZnO nanorods at low volume (weight) fractions (< 2.9% v/v (17.75% w/w)). Tensile modulus enhancements were modest though, comparable to values observed for spherical nanofillers. Shape memory characteristics, which in this LHS-TPU result when strain-induced crystallites retard the entropic recovery of the deformed chains, were unchanged for these low volume fraction ZnO nanocomposites. Higher ZnO loadings (12% v/v (50% w/w)) exhibited clustering of ZnO nanorods into a mesh-like structure. Here, tensile modulus and shape recovery characteristics were improved, although not as great as seen for comparable CNF addition. Wide angle X-ray diffraction and NMR revealed that the addition of ZnO nanorods did not impact the inherent strain induced crystallization of the LHS-TPU, which is in contrast to the impact of CNFs and emphasizes the impact of interactions at the polymer-nanoparticle interface. Overall, these findings reinforce the hypothesis that the shape memory properties of polymer nanocomposites are governed by the extent to which nanoparticle addition, via nanoparticle aspect ratio, hierarchical morphology, and interfacial interactions, impacts the molecular mechanism responsible for trapping elastic strain.