PHYSICAL REVIEW E 84, 011604 (2011)
Effect of polymer on the elasticity of surfactant membranes: A light scattering study
Ram´ on I˜ niguez-Palomares, Heriberto Acu˜ na-Campa, and Amir Maldonado
Departamento de F´ ısica, Universidad de Sonora, 83000 Hermosillo, Sonora, Mexico
(Received 21 August 2010; published 8 July 2011)
We have performed a dynamic light-scattering (DLS) investigation of the effect of a water-soluble polymer,
polyethylene glycol (PEG), on the bending elastic modulus κ of surfactant membranes. The polymer, in
concentrations ranging from 0 to 8 g/L (0 to 0.4 mM), was incorporated into the solvent of sponge phases of
the sodium dodecyl sulfate (SDS)-hexanol-brine system. PEG adsorbs into the SDS membranes. The correlation
functions of the polymer-doped sponge phases displayed a stretched-exponential decay, appropriately described
by the Zilman-Granek (Z-G) theory for fluctuating membranes. The dynamics of the surfactant bilayers was
slowed down by the addition of the polymer: Increasing PEG concentrations increase the DLS relaxation times.
From the Z-G model we extracted the membrane-bending elastic modulus, as a function of polymer concentration,
C
PEG
= κ increases with C
PEG
, a behavior opposite to that expected from available models for the interaction
between fluid membranes and adsorbing polymers. Our results suggest that the polymer penetrates to some extent
the surfactant bilayers.
DOI: 10.1103/PhysRevE.84.011604 PACS number(s): 68.15.+e, 82.70.Uv, 87.64.Cc
I. INTRODUCTION
Surfactants in solution give rise to different equilibrium
phases [1], depending on the values of the physicochem-
ical variables (concentration, temperature, concentration of
additives, etc.). There are two basic local structures: mi-
celles (spherical or cylindrical) and bilayers (membranes). In
both cases the hydrophobic tail of the surfactant molecule
avoids water contact by hiding in the interior of the
structure.
Bilayers in aqueous solutions are formed by two surfactant
monolayers facing each other through their hydrophobic
moieties. At a larger scale, surfactant bilayers can adopt
several configurations. Two of the most common are the
so-called lamellar [2] and sponge phases [3]. In the first
case, the membranes arrange in a parallel stack of fluctuating
bilayers separated by solvent; the system is characterized by
the interbilayer distance d and the bilayer thickness δ, related
through the surfactant volume fraction φ by the classical
dilution law φ = δ/d.
On the other hand, the sponge phase (Fig. 1) is a disordered
array of bilayers continually connected in the three dimen-
sions; this phase can be pictured as a structure containing
pores or passages separating two equivalent volumes of
solvent. A characteristic distance d is measured in appropriate
static scattering experiments; it can be interpreted as a mean
interbilayer distance or as the mean diameter of the pores in
the structure. In the sponge phase, d is also related to the
bilayer thickness by the dilution law: φ = αδ/d, where α
depends on the topology of the phase and has a value near
to 1.5.
It is interesting to study and understand the properties
of lamellar or sponge phases doped with polymers of dif-
ferent chemical characteristics: water-soluble, nonadsorbing
polymers, adsorbing polymers, or amphiphilic polymers. The
interaction between surfactant structures and polymers is of
interest because of the applications of the mixed systems.
Surfactants are relevant in detergency, wetting, foaming, or
emulsification, while polymers are usually added to control
the viscosity of the solutions. The phase behavior as well
as the physical properties of these systems strongly depend
on the polymer-membrane interactions. In the literature there
are several reports, both experimental [4–20] and theoretical
[21–25], on the effect of polymers on lamellar or sponge
phases.
For instance, in a previous work, it has been shown that
the addition of polyethylene glycol (PEG) to the lamellar or
sponge phase of the sodium dodecyl sulfate (SDS)-hexanol-
brine system produces the appearance of a vesicular phase in
coexistence with excess solvent [20]. The actual mechanism
of this transformation is not completely understood so far,
but one can argue that the polymer modifies the Gaussian
elastic constant of the surfactant bilayers and thus triggers a
topological phase transformation. In order to obtain a better
insight into the mechanism of the reported lamellar (sponge)-
vesicular transformation, it is interesting to study the elastic
properties of the membranes of this system, as a function of
polymer concentration.
In this context, we have carried out a systematic light-
scattering study of the effect of increasing concentrations of
PEG on the bending elastic modulus of SDS-hexanol-brine
sponge phases. The experimental results are reported in this
paper. The aim is to understand the effect of the polymer on
the elastic properties of the surfactant membranes.
The paper is organized as follows. In the next section we
provide a brief theoretical as well as experimental background
to our work. In Sec. III we give the details of our experiments.
In Sec. IV we present and discuss our results. Finally, in Sec. V
we draw conclusions of our investigation. In the supplementary
material, we present related experimental results obtained for
our system [40].
II. BACKGROUND
A. Bilayer elastic constants
The elastic properties of surfactant membranes can be
described by the bending elastic modulus κ and the Gaussian
011604-1 1539-3755/2011/84(1)/011604(6) ©2011 American Physical Society