A Micellar Sphere-to-Cylinder Transition of Poly(ferrocenyldimethylsilane-b-2-vinylpyridine) in a Selective Solvent Driven by Crystallization

ABSTRACT: A sample of poly(ferrocenyldimethylsilane)-b-poly(2-vinylpyridine) (PFS23-b-P2VP230), with a short PFS block and a P2VP block 10-fold higher in degree of polymerization, forms spherical micelles when dissolved in ethanol. Over time (hours, days, and weeks), these solutions undergo a micelle sphere-to-cylinder transition eventually forming rather stiff, uniform fiber-like micelles with a core width of 10 nm, lengths between 20 and 50 µm, and approximately four polymer molecules per nm length. Here, we report the results of a combination of transmission electron microscopy, wide-angle X-ray scattering (WAXS), as well as static and dynamic laser light scattering measurements to follow the structural evolution. One key observation is the onset of partial aggregation of spherical micelles after an initial induction period (hours), so that the system as it ages consists of mixtures of free spherical micelles, micelle aggregates, and elongated structures with a high aspect ratio. Another important observation is the growth in intensity and sharpness of the WAXS peak characteristic of crystalline PFS domains as the number and uniformity of the cylindrical micelles increases. This formation of crystalline domains is the likely driving force for the structural transformation