Two-Step Freezing in Alkane Monolayers on Colloidal Silica Nanoparticles: From a Stretched-Liquid to an...

The crystallization behavior of an archetypical soft/hard hybrid nanocomposite, that is, an n-octadecane C18/SiO2-nanoparticle composite, was investigated by a combination of differential scanning calorimetry (DSC) and variable-temperature solid-state (13)C nuclear magnetic resonance (VT solid-state (13)C NMR) as a function of silica nanoparticles loading. Two latent heat peaks prior to bulk freezing, observed for composites with high silica loading, indicate that a sizable fraction of C18 molecules involve two phase transitions unknown from the bulk C18. Combined with the NMR measurements as well as experiments on alkanes and alkanols at planar amorphous silica surfaces reported in the literature, this phase behavior can be attributed to a transition toward a 2D liquid-like monolayer and subsequently a disorder-to-order transition upon cooling. The second transition results in the formation of a interface-frozen monolayer of alkane molecules with their molecular long axis parallel to the nanoparticles' surface normal. Upon heating, the inverse phase sequence was observed, however, with a sizable thermal hysteresis in accord with the characteristics of the first-order phase transition. A thermodynamic model considering a balance of interfacial bonding, chain stretching elasticity, and entropic effects quantitatively accounts for the observed behavior. Complementary synchrotron-based wide-angle X-ray diffraction (WAXD) experiments allow us to document the strong influence of this peculiar interfacial freezing behavior on the surrounding alkane melts and in particular the nucleation of a rotator phase absent in the bulk C18.