When
an insoluble surfactant is deposited on the surface of a thin
fluid film, stresses induced by surface tension gradients drive Marangoni
spreading across the subphase surface. The presence of a predeposited
layer of an insoluble surfactant alters that spreading. In this study,
the fluid film was aqueous, the predeposited insoluble surfactant
was dipalmitoylphosphatidylcholine (DPPC), and the deposited insoluble
surfactant was oleic acid. An optical density-based method was used
to measure subphase surface distortion, called the Marangoni ridge,
associated with propagation of the spreading front. The movement of
the Marangoni ridge was correlated with movement of surface tracer
particles that indicated both the boundary between the two surfactant
layers and the surface fluid velocities. As the deposited oleic acid
monolayer spread, it compressed the predeposited DPPC monolayer. During
spreading, the surface tension gradient extended into the predeposited
monolayer, which was compressed nonuniformly, from the deposited monolayer.
The spreading was so rapid that the compressed predeposited surfactant
could not have been in quasi-equilibrium states during the spreading.
As the initial concentrations of the predeposited surfactant were
increased, the shape of the Marangoni ridge deformed. When the initial
concentration of the predeposited surfactant reached about 70 A2/molecule, there was no longer a Marangoni ridge but rather
a broadly distributed excess of fluid above the initial fluid height.
The nonuniform compression of the annulus of the predeposited monolayer
also caused tangential motion ahead of both the Marangoni ridge and
the boundary between the two monolayers. Spreading ceased when the
two monolayers reached the same final surface tension. The final area
per molecule of the DPPC monolayer matched that expected from the
equilibrium DPPC isotherm at the same final surface tension. Thus,
at the end of spreading, there was a simple surface tension balance
between the two distinct monolayers.
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