Adsorption of Block Copolymers in Nanoporous Alumina

We have studied the adsorption of end-attaching block copolymer chains inside the cylindrical pores of nanoporous alumina. Highly asymmetric PS-PEO block copolymers, with a small PEO anchoring block and a long PS dangling block, were allowed to adsorb onto porous alumina substrates with an average pore diameter of similar to 200 nm from toluene solution. The adsorption process was monitored using FTIR spectroscopy, whereas depth profile analysis was performed by means of XPS and Ar+ ion sputtering. It is found that the PS-PEO adsorption kinetics in porous alumina are 4 orders of magnitude slower than the corresponding case of a flat alumina substrate. It appears that chains adsorbed near the pore entrance early on tend to form a barrier for chains entering the pore at later times, thereby slowing down the adsorption process significantly. This effect is much more pronounced for large chains whose dimensions are comparable with the pore diameter. The equilibrium adsorbance value is also affected by chain size due to the additional entropic penalty associated with chain confinement, the adsorbance falling substantially when the chain dimensions become comparable with the pore diameter. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1676-1682, 2010