Langmuir, Vol.19, No.7, 2795-2801, 2003
Dynamics of partial wetting and dewetting of an amorphous fluoropolymer by pure liquids
We report velocity dependencies of dynamic contact angles for CCl4 and tert-butyl alcohol on the amorphous fluoropolymer AF 1600 and compare them with our previous results for octamethylcyclotetrasiloxane (OMCTS) on the same substrate. The molecules of these liquids have well-defined form and the solid surface is almost smooth and homogeneous, which enables checking the assumptions of the main theories of wetting dynamics. We find that the molecular-kinetic theory well represents the data for CCl4 in the characteristic cos Theta/V scale but qualitatively disagrees with the experiment for tert-butyl alcohol and OMCTS at high velocities. The CCl4 data do not fulfill the requirement of the hydrodynamic theory for symmetric advancing and receding branches. For the other two systems, the hydrodynamic theory works better at high velocities, but the nonlinear initial sections of the Theta(3)/V plots require consideration of the velocity dependence of the microscopic dynamic contact angle Theta(c)(V). This is done by the molecular-hydrodynamic theory accounting for both contact line and bulk viscous friction. This theory shows agreement with the experimental data in the entire velocity range for all systems compared. It fits the receding and advancing Theta/V branches simultaneously, yielding unique values of the microscopic dynamic parameters lambda, K-o,K-s, and L-c,L-max that do not depend on direction of the contact line motion. Only this theory describes the wetting-dewetting asymmetry observed for tert-butyl alcohol and OMCTS. However, it yields inadequately large values of lambda and too small hopping frequencies K-o,K-s for CCl4 and tert-butyl alcohol. Such results, also reported previously, might mean that not lambda and K-o,K-s but their combinations better serve for description of wetting dynamics. Here we analyze the characteristic molecular-kinetic velocity V-o,V-s = lambdaK(o,s) and the coefficient of friction of a unit contact line length xi(c) = kT/K(o,s)lambda(3) and find a significant difference between the studied systems.