Theresa A. LaFollette and Lynn M. Walker. Carnegie Mellon University, Pittsburgh, PA
Hydrophilic nanoparticles have recently been templated into the interstitial spaces of close-packed micelle gel structures in Pluronic block copolymers to successfully form nanocomposites. Previous work has focused on nanocomposite systems consisting of soft crystals of cubic packed spherical micelles with bovine serum albumin (BSA) and lysozyme as model monodisperse nanoparticles. Nanoscale structure is determined from small angle neutron scattering (SANS) and the mechanical properties of the nanocomposites are studied with oscillatory rheology. The pluronic P123 (PEO20-PPO70-PEO20) forms both a cubic packed spherical micelle phase and a hexagonally packed cylindrical micelle phase. An anisotropic phase transition has been observed between the cubic packed spherical micelle phase and the hexagonally packed cylindrical micelle phase at both the macroscale in rheology experiments and the nanoscale in SANS. The cubic nanoscale order persists after the phase transition to the hexagonally packed cylindrical micelle phase demonstrating that the pluronic gel has nanoscale thermal memory. It has also been observed that these thermal history effects can only be seen in the nanoscale structure of the ordered cylindrical micelle gel and not the nanoscale structure of the ordered cubic micelle gel. Nanocomposites of P123 with proteins incorporated in the gel also show this thermal history with a similar anisotropic phase transition. SANS experiments in both the cubic packed spherical micelle phase and the hexagonally packed cylindrical micelle phase demonstrate that shear is needed to align the grain boundaries found in the soft micelle packed gel to form a highly ordered soft crystal. Oscillation alone was not enough to create a high level of order at the nanoscale. The static nanostructures, thermal transitions and shear alignment will be discussed and quantified.