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A new pathway for the re-equilibration of micellar surfactant solutions
Micellar surfactant solutions are generally assumed to undergo restructuring via stepwise monomer loss following a dilution. This process is captured by the Becker-Döring equations, an infinite-dimensional system of ordinary differential equations for the concentration of each aggregate in solution....
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Published in: | Soft matter 2013-01, Vol.9 (3), p.853-863 |
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Main Authors: | , , , , , |
Format: | Article |
Language: | English |
Subjects: | |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | Micellar surfactant solutions are generally assumed to undergo restructuring
via
stepwise monomer loss following a dilution. This process is captured by the Becker-Döring equations, an infinite-dimensional system of ordinary differential equations for the concentration of each aggregate in solution. We reveal certain classes of surfactants, such as the non-ionic family C
n
E
m
, for which the predicted re-equilibration times
via
stepwise monomer loss are far greater than those observed experimentally. We investigate two alternative pathways for re-equilibration, first allowing for micelles to break down into two aggregate fragments rather than stepwise monomer release, and secondly by allowing aggregates to merge together to form large
super-micelles
that exceed the size of a proper micelle. While the former shows no discernible difference in the predicted time to re-equilibration, the latter provides an alternative pathway to re-equilibration: the formation of unstable super-micelles that break down to proper micelles
via
a cascade of stepwise monomer release. The new theory is shown to describe the re-equilibration of
any
surfactant system, with the conventional Becker-Döring theory forming a subset of the model that describes the behaviour of a small range of surfactant systems with high critical micelle concentrations and low aggregation numbers. The pathway proposed provides an essential mechanistic route to equilibrium.
Evolution of monomer concentration,
X
1
, to the CMC (
X
1
= 1) with time illustrating the effect of allowing super-micelle formation. |
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ISSN: | 1744-683X 1744-6848 |
DOI: | 10.1039/c2sm27154k |