Crust Effect on Multiscale Pattern Formations in Drying Micelle Solution Drops on Solid Substrates

Spherical micelles of a polystyrene-b-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer with the number-average molecular weight of 193 000 g/mol for PS and 39 000 g/mol for PDMS were obtained by using n-dodecane or n-octane as the selective solvent for the PDMS block. The drying process of micelle solution drops with relatively high polymer concentration on solid substrates and the resultant drying patterns were studied using optical microscopy and atomic force microscopy. The drying drops exhibited an inner solution "cap" connecting with an outer gelled "foot" through a transition zone. A crust was first formed on the surface of the transition zone and remained on the top of the foot region. An inhomogeneous stress perpendicular to the radial direction within the crust, which was due to the solvent evaporation accompanied by the receding of the solution cap, induced regular 45 degrees -tilted stripes (pleats) in the transition zone and main radial cracks in the foot region. The stripes and cracks have periods of a few and tens of microns, respectively. Concave micelle "bricks" were also observed between cracks. In addition to micelle close packing, these patterns demonstrate that drying micelle solution drops may provide a potential means to manipulate fine and multiscale structures for technological applications.