Influence of Confinement on the Chain Conformation of Cyclic Poly(N‑isopropylacrylamide)

In thin and ultrathin supported films, the conformations of flexible linear polymer chains might be considerably confined, in particular, for film thicknesses smaller than a few times the radius of gyration. For ring polymers in solution or in melt, the radii of gyration are significantly reduced as compared to those of their linear counterparts. We study here the influence of geometrical confinement on the chain conformation of cyclic PNIPAM in silicon-supported films. Measurements are performed by grazing incidence small angle neutron scattering (GISANS). For all films, the component of the radius of gyration parallel to the substrate, R_gc∥, is significantly higher than the unperturbed R_gc determined under theta solvent or melt conditions. We attribute this effect to a preferential selection of stretched PNIPAM ring conformations in thin films and a preferential orientation of macromolecules parallel to the film interfaces with the substrate and air.