Conformation mediated preferential swelling of amphiphilic block copolymer ultrathin films

Abstract : Steady-state and dynamic swelling characteristics of PEO-PPO-PEO copolymer ultrathin films comprising 2-layered structure, where the bottom layer (L1) is made of one PEO (hydrophilic)-PPO (hydrophobic) bilayer and the top layer (L2) is made of two alternating PEO-PPO bilayers, have been studied at room temperature in precisely controlled environment of 10–93% relative humidity (RH). Swelling, which is monitored by measuring the thickness of the films using X-ray reflectivity (XRR), is found to be largely dissimilar in differently thick films prepared by varying the concentration of mother solutions from 1 g/L to 4 g/L. This is well explained considering a preferential-swelling of amphiphilic block copolymer, where only the hydrophilic PEO blocks contribute in swelling and PPO acts a barrier in the diffusion of water molecules. The swelling kinetics is governed by the thickness/width and coverage of outer PPO block layer.