Moving contact lines in liquid/liquid/solid systems

A general mathematical model which describes the motion of an interface between immiscible viscous fluids along a smooth homogeneous solid surface is examined in the case of small capillary and Reynolds numbers. The model stems from a conclusion that the Young equation, sigma(1) cos theta = sigma(2) - sigma(3), which expresses the balance of tangential projections of the forces acting on the three-phase contact line in terms of the surface tensions sigma(i) and the contact angle theta, together with the well-established experimental fact that the dynamic contact angle deviates from the static one, imply that the surface tensions of contacting interfaces in the immediate vicinity of the contact line deviate from their equilibrium values when the contact line is moving. The same conclusion also follows from the experimentally observed kinematics of the flow, which indicates that liquid particles belonging to interfaces traverse the three-phase interaction zone (i.e. the 'contact line') in a finite time and become elements of another interface - hence their surface properties have to relax to new equilibrium values giving rise to the surface tension gradients in the neighbourhood of the moving contact line. The kinematic picture of the flow also suggests that the contact-line motion is only a particular case of a more general phenomenon - the process of interface formation or disappearance - and the corresponding mathematical model should be derived from first principles for this general process and then applied to wetting as well as to other relevant flows. In the present paper, the simplest theory which uses this approach is formulated and applied to the moving contact-line problem. The model describes the true kinematics of the flow so that it allows for the 'splitting' of the free surface at the contact line, the appearance of the surface tension gradients near the contact line and their influence upon the contact angle and the flow field. An analytical expression for the dependence of the dynamic contact angle on the contact-line speed and parameters characterizing properties of contacting media is derived and examined. The role of a 'thin' microscopic residual film formed by adsorbed molecules of the receding fluid is considered. The flow field in the vicinity of the contact line is analysed. The results are compared with experimental data obtained for different fluid/liquid/solid systems.