While
the concept of interfacial tension synergism in surfactant
mixtures is well established, little attention has been paid to the
possibility of synergistic effects on the interfacial rheology of
mixed surfactant systems. Furthermore, interfacial tension synergism
is most often investigated for mixtures of surfactants residing in
a single phase. Here, we define dilatational modulus synergism and
report a study of interfacial tension isotherms and complex dilatational
moduli for a binary surfactant system with the two surfactants accessing
the oil/water interface from opposite sides. Using an oil-soluble
fatty acid surfactant (palmitic acid, PA) that may be ionized at the
oil/water interface and a quaternary ammonium water-soluble cationic
surfactant (tetradecyltrimethylammonium bromide, TTAB), the binary
interfacial interaction was tuned by the aqueous phase pH. Interfacial
tensions and dilatational moduli were measured by the pendant drop
method for the binary surfactant system as well as the corresponding
single-surfactant systems to identify synergistic effects. The possible
occurrence of dilatational modulus synergism was probed from two perspectives:
one for a fixed total surfactant concentration and the other for a
fixed interfacial tension. The aqueous pH was found to have a controlling
effect on both interfacial tension synergism and the dilatational
modulus synergism. The conditions for interfacial tension synergism
coincided with those for the storage modulus synergism: both tension
and storage modulus synergisms were observed under all conditions
tested at pH 7 where PA was mostly deprotonated, for both perspectives
examined, but not for any conditions tested at pH 3 where PA is mostly
protonated. The loss modulus synergism exhibited more complex behaviors,
such as frequency and interfacial tension dependences, but again was
only observed at pH 7. The tension and modulus synergism at pH 7 were
attributed to the increased attraction between ionized PA and cationic
TTAB and the formation of catanionic complexes at the oil/water interface.