Self-assembly of ternary and 5-component surfactant mixtures studied.

In ternary mixtures, scattering data modelled as globular interacting micelles.

In ternary mixtures, variation in aggregation number implies micelle composition close to solution composition.

In 5-component mixture addition of rhamnolipid biosurfactants affects evolution in phase behaviour.

For rhamnolipid rich compositions transition from micelle to lamellar/micellar co-existence occurs.

Transition associated with synergistic packing effects.