A lubrication analysis is presented for the near-contact axisymmetric
motion of
spherical drops covered with an insoluble non-diffusing surfactant. Detailed
results
are presented for the surfactant distribution, the interfacial velocity,
and the gap width
between the drop surfaces. The effect of surfactant is characterized by
a dimensionless
force parameter: the external force normalized by Marangoni stresses. Critical
values
of the force parameter have been established for drop coalescence and separation.
Surfactant-covered drops are stable to rapid coalescence for external forces
less than
4πkTac0, where c0 is the
surfactant concentration at the edge of the near-contact
region and a is the reduced drop radius.
For subcritical forces, the behaviour of surfactant-covered drops is
described by two
time scales: a fast time scale characteristic of near-contact motion between
drops with
clean interfaces and a slow time scale associated with rigid particles.
The surfactant
distribution evolves on the short time scale until Marangoni stresses approximately
balance the external force. Supercritical values of the external force
cannot be balanced;
coalescence and separation occur on the fast time scale. The coalescence
time
normalized by the result for drops with clean interfaces is independent
of the viscosity
ratio and initial gap width.
Under subcritical force conditions, a universal long-time behaviour
is attained on
the slow time scale. At long times, the surfactant distribution scales
with the
near-contact region and the surface velocity is directed inward which impedes
the drop
approach and accelerates their separation compared to rigid particles.
For drops
pressed together with a sufficiently large subcritical force, a shrinking
surfactant-free
clean spot forms.
Surfactant-covered drops exhibit an elastic response to unsteady external
forces
because of energy stored in the surfactant distribution.