Effect of Grafting Density on Phase Transition Behavior for Poly(N-isopropylacryamide) Brushes in Aqueous Solutions Studied by AFM and QCM-D

The effect of grafting density on the phase transition behavior of poly(N-isopropylacrylamide) (PNIPAM) grafted onto a flat substrate was investigated using an atomic force microscope (AFM) and a quartz crystal microbalance (QCM-D). We prepared PNIPAM brush layers at three different grafting densities on silicon wafers using a "grafting from" atom transfer radical polymerization (ATRP) approach. AFM imaging in water at various temperatures showed that the transition behavior of the grafted PNIPAM chains from a brush-like to a mushroom-like morphology was dependent on the grafting density: the images change abruptly from essentially featureless to domain structures across the LCST for the low-density surface, whereas the change in the images becomes less abrupt with increasing polymer graft density. The QCM-D data also indicated a significant dependence of the layer properties on the grafting density, confirming the behavior differences suggested by the AFM images. In particular, the dissipation data strongly suggest that the magnitude of lateral aggregation for the PNIPAM chains depends on the grafting density. A similar effect of grafting density was also observed for the phase transition as a function of salt concentration in sodium sulfate solutions.