Magnetic Microrheology of Block Copolymer Solutions

The viscosity of poly(styrene)-b-poly(lactide) [PS-b-PLA] solutions in a neutral solvent was characterized by magnetic microrheology. The effect of polymer concentration on the viscosity of the block polymer solutions was compared with that of the PS and PLA homopolymers in the same solvent. The viscosity of PS-b-PLA solution, unlike the homopolymer solutions, showed a steep increase over a narrow concentration range. The steep rise was concomitant with microphase separation into an ordered cylindrical microstructure as determined by small-angle X-ray scattering. Hence microrheology proved effective as a means of characterizing the order-disorder transition concentration. During an in situ drying experiment, changes in local viscosity through the depth of a block copolymer solution were characterized as a function of drying time. Early in the drying process, the viscosity rose steadily and was uniform through the depth, a result consistent with steadily increasing and uniform polymer concentration. However, later in the drying process as the overall polymer concentration approached that required for microphase separation, the viscosity of the polymer solution near the free surface became an order of magnitude higher than that near the bottom of the container. The zone of high viscosity moved downward as drying proceeded, consistent with a microphase separation front.