The
intriguing ability of certain surfactant molecules to drive
the superspreading of liquids to complete wetting on hydrophobic substrates
is central to numerous applications that range from coating flow technology
to enhanced oil recovery. Despite significant experimental efforts,
the precise mechanisms underlying superspreading remain unknown to
date. Here, we isolate these mechanisms by analyzing coarse-grained
molecular dynamics simulations of surfactant molecules of varying
molecular architecture and substrate affinity. We observe that for
superspreading to occur, two key conditions must be simultaneously
satisfied: the adsorption of surfactants from the liquid–vapor
surface onto the three-phase contact line augmented by local bilayer
formation. Crucially, this must be coordinated with the rapid replenishment
of liquid–vapor and solid–liquid interfaces with surfactants
from the interior of the droplet. This article also highlights and
explores the differences between superspreading and conventional surfactants,
paving the way for the design of molecular architectures tailored
specifically for applications that rely on the control of wetting
