Journal of Chemical Physics, Vol.103, No.12, 5137-5143, 1995
Effect of Chain-Length and Surface-Density on Looped Polymers Grafted to an Impenetrable Surface
Chemical modification of inorganic surfaces through the use of grafted polymers constitutes an important means by which to tailor surface properties. While numerous theoretical and simulation efforts have addressed dense, single-grafted polymer layers (i.e., brushes), few have sought to examine layers comprised of double-tethered macromolecules (i.e., loops). In this work, bond-fluctuation (BF) simulations have been performed in the presence of an impenetrable surface and good solvent to ascertain the effect of surface anchor density (sigma) and chain length (N) on the segmental density distribution and layer thickness of grafted polymer loops. At low sigma, the density distribution for loops is accurately described by self-consistent field (SCF) theories for brushes of half-chain length, whereas the parabolic form of the SCF distributions is replaced by a blocklike profile, indicative of density saturation, at high sigma. For N>20, the a signaling the onset of chain impingement is found to obey the same scaling relationship as that of blushes, namely, N--6/5 Median segment density distributions for grafted loops at low sigma are comparable to SCF tail-end distributions of half-length brushes but again, due to density saturation, deviate from SCF predictions at high sigma.
Keywords:CONSISTENT-FIELD-THEORY;TERMINALLY ATTACHED CHAINS;MONTE-CARLO SIMULATION;COPOLYMER ADSORPTION;MOLECULAR-DYNAMICS;ADSORBED POLYMER;BRUSHES;STABILIZATION;INTERFACE;PROFILE