38 research outputs found
Superspreading: Mechanisms and Molecular Design
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
Surfactants at the design limit
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Langmuir, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.langmuir.5b00336This article analyzes how the individual structural elements of surfactant molecules affect surface properties, in particular, the point of reference defined by the limiting surface tension at the aqueous cmc, γcmc. Particular emphasis is given to how the chemical nature and structure of the hydrophobic tails influence γcmc. By comparing the three different classes of surfactants, fluorocarbon, silicone, and hydrocarbon, a generalized surface packing index is introduced which is independent of the chemical nature of the surfactants. This parameter ϕcmc represents the volume fraction of surfactant chain fragments in a surface film at the aqueous cmc. It is shown that ϕcmc is a useful index for understanding the limiting surface tension of surfactants and can be useful for designing new superefficient surfactants