  We study the effect of physical confinement on the capillary infiltration of
polymers into cylindrical nanopores using molecular dynamics simulations. In
particular, we probe whether the critical contact angle above which capillary
rise infiltration ceases to occur changes for long chain polymers, possibly due
to loss of conformation entropy induced by chain confinement. Surprisingly, the
critical contact angle does not strongly depend on the length of polymer chains
and stays constant for large N. A free energy model is developed to show that
the critical angle for infiltration depends strongly on the size of statistical
segments rather than the total chain length, which we confirm by performing MD
simulations of infiltration with semi-flexible polymers. These results could
provide guidelines in manufacturing polymer nanostructures and nanocomposites
using capillary rise infiltration.
