Colloids and Surfaces

A: Physicochemical and Engineering Aspects 167 (2000) 189 – 197

www.elsevier.nl/locate/colsurfa

Mixed monolayers of polyelectrolytes and surfactants at the

air–water interface
A. Asnacios a, R. Klitzing b, D. Langevin c,*
a
Laboratoire de Physique des Matériaux Di6isés, Uni6ersité de Marne-la-Vallée (IFI) Descartes Cité, Champs sur Marne,
77454 Marne la 6allée cedex 2, France
b
Iwan-N-Stranski Institute, Technical Uni6ersity of Berlin, Strasse des 17 juni 112, W-1000 Berlin 12, Germany
c
Laboratoire de Physique des Solides, Uni6ersité Paris sud, Bâtiment 510, 91405 Orsay, France

Abstract

Dilute mixed solutions of non surface active anionic polymers (polyacrylamide and polystyrene sulfonate) and
various surfactants have been studied with several methods: surface tension, ellipsometry, surface and bulk rheology.
A strong synergistic lowering of the surface tension is found with cationic surfactants in the concentration range
where no appreciable complexation of surfactant and polymer occurs in the bulk solution (as seen from viscosity
measurements). A simple adsorption model, in which it is assumed that both polymer and surfactant counterions are
expelled away from the surface, is in good agreement with the observations on polyacrylamide sulfonate. The
behaviour of the more hydrophobic polystyrene sulfonate is very different and still not understood. The behaviour of
this polymer with nonionic surfactants is also different. The connection of foam stability with surface and bulk
complexation is discussed. © 2000 Elsevier Science B.V. All rights reserved.

Keywords: Anonic polymers; Non surface active; Foam stability

1. Introduction ing rheological properties. Biological membranes

Interactions between surfactants and polymers
is a rapidly growing field of interest in colloid
science [1]. Many practical systems for industrial
applications contain mixtures of polymers and
surfactants, which are widely used as thickeners in
water based formulations such as paints, drilling
muds, etc. In these applications, polyelectrolytes
are of particular interest, because of their interest-
* Corresponding author. Tel.: +33-1-69155351; fax: + 33-
1-69156086.
E-mail address: langevin@1ps.u-psud.fr (D. Langevin)
are structured complexes of lipids and proteins,
which are also charged polymers. Whereas there is
an extensive literature on surfactant solutions on
one hand, and polymer solutions on the other
hand, much less is known for the mixed solutions.
Polyelectrolyte solutions are less well understood
than neutral polymer solutions, but recent work
has enhanced the current knowledge [2]. These
polymers form more extended structures than
neutral polymers, with effective persistence
lengths much larger than those of neutral poly-
mers. The polyelectrolyte solutions are in the

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190 A. Asnacios et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 189–197
semi-dilute range at very small polymer concen-
trations; however, the viscosity of the solutions
remains small because the polymer chains are
rod-like and less entangled. The influence of the
counterions is subtle: partial counterion conden-
sation frequently occurs and the concentration of
counterions is enhanced close to the polyion.
When two polyelectrolytes of opposite charge are
mixed, the two polyions associate, thus releasing
the counterions in the solution, and increasing the
entropy of the solution [3]. It was observed that
the behaviour of polyelectrolyte – surfactant solu-
tions is similar to the behaviour of polyelec-
trolyte-polymer solutions: no association when
the surfactant or the polymer are nonionic or
when the two species have the same charge, and
strong association for opposite charges. The case
of surfactant-polymer mixtures is however, less
simple, because the size and the shape of the
surfactant aggregates can vary.
Polymers and surfactants also form complexes
at surfaces, either solid – fluid or fluid – fluid sur-
faces. Complexation in bulk or at a surface are
generally related [4]. Surface complexation is also
important for practical applications such as col-
loidal stabilization, wettability, adhesion, etc.
New materials where the mechanical strength of
the polymer and the selective barrier of lipid
bilayers are coupled are made with lipids and
polymers of opposite charges. [5] Only few studies
have focused on surfactant-polyelectrolyte com-
plexation at a surface. Several recent ones address
the problem of polyelectrolyte complexation with
insoluble monolayers [6 – 8,24]. In this paper we
present a study of polymer-surfactant complexa-
tion at the free surface of an aqueous solution, the
surfactants being soluble. This case is frequent in
practice, but more difficult to analyse: indeed,
contrary to insoluble monolayers, the amount of
surfactant adsorbed at the surface is not known
and has to be either measured, or inferred from
thermodynamic models. We have studied two
model polymers: polacrylamide and polystyrene
partially sulfonated, with a degree of sulfonation
x, defined as the molar ratio of sulfonated
monomers to neutral monomers. The first poly-
mer is water soluble regardless the value of x,
whereas polystyrene sulfonate is water soluble
only if x\ 0.3 [9,25]. This is because the back-
bone is more hydrophobic, and as we will see
later, this leads to significant differences in surface
behavior. We have characterised the bulk com-
plexation by viscosity measurements, and the sur-
face complexation by surface tension, ellipsometry
and surface rheology measurements.
2. Experimental section
2.1. Materials
The cationic surfactants, dodecyl and hexadecyl
trimethyl ammonium bromides (DTAB and
CTAB) from Aldrich were recrystallized three
times before use. The nonionic surfactants, alkyl
pentaethylene glycol ethers (C10E5 and C12E5)
from Nikko were used as supplied.
The polyacrylamide sulfonate (PAMPS), syn-
thetized by SNF Floerger, is a statistical copoly-
mer composed of neutral monomers of
acrylamide (AM) and charged monomers of acry-
lamido methyl propane sulfonate (AMPS). Two
different molecular weights were studied, Mw =
2.2× 106 and Mw = 4× 105. For Mw = 2.2×106,
2 degrees of charge were investigated: x=25 and
10%. Polystyrene sulfonate (PSS) is a statistical
copolymer made of polystyrene and polystyrene
sulfonate monomers. It was obtained by postsul-
fonation of polystyrene of molecular weight of
2.5× 105 in the laboratory of F.Lafuma (ESPCI,
Paris) with variable degrees of sulfonation [9,25].
A fully sulfonated compound was also obtained
from Aldrich, Mw = 70 000. To eliminate any
traces of surfactant molecules and low molecular
weight impurities, the polymer solutions were
passed through an ultrafiltration unit with a
20 000 cut-off membrane. After this purification,
the polymers display no surface activity at con-
centrations below 1000 ppm.
2.2. Methods
Surface tension measurements were performed
at room temperature. The surface tension was
measured with an open frame version of the Wil-
helmy plate (to avoid the wetting problems of the
 A. Asnacios et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 189–197
classical plate). For mixed solutions at low surfac-
tant concentrations and polyelectrolytes of large
molecular weight, the approach to equilibrium
could take several hours and it was assumed
arbitrarily that equilibrium had been reached
when the surface tension variation was less
than 0.01 mN/m over 10 min. The reproducibility,
including long equilibration time and/or con-
tamination effects, was 0.5 mN/m for mixed solu-
tions.
Viscosities of polymer solutions and mixed
polymer-surfactant solutions were measured using
a low shear viscosimeter (Contraves 30) which has
a coaxial cylindrical geometry. The shear thinning
behaviour of the polymer has been characterized
and all subsequent measurements have been done
at low shear rates, below 0.5 inverse seconds.
Surface viscosities and elasticities were measured
with a home-built instrument where capillary
waves are excited with a sinusoidal voltage and
detected by surface optical profilometry. The vis-
coelastic parameters are deduced from the propa-
gation characterics differences between solutions
and pure water [10].
Ellipsometric angles were measured by means
of a PLASMOS (SD 2300) rotating-analyzer ellip-
someter. The thickness d and the refractive index
nd of the adsorbed layer are deduced from the
ellipsometric angles variations between the surface
of the solution and pure water. For the layers
studied here, the thicknesses are very small and
one of the two angles is of the order of the
experimental accuracy. It is then important to
check the consistency of the values of d and nd
determined by this way, with those obtained from
a different analysis based on the second angle and
the determinations of area per molecule from the
Gibbs equation [11].
3. Results and discussion
We have worked with polymer/surfactant
solutions of fixed polymer concentration and vari-
able surfactant concentrations. We have thus
studied the changes induced by the presence of
fixed amounts of polymer in the surfactant solu-
tions.
191
3.1. Non ionic and anionic surfactants
The surface tension of mixed solutions of C10E5
and PAMPS or fully sulfonated PSS does not
differ from the surface tension of the polymer-free
surfactant solutions [11,12]. For the partially sul-
fonated PSS, a large surface tension increase is
observed (Fig. 1) [12]. This is similar to the behav-
ior of mixed solutions with a similar surfactant,
C12E6, and a water soluble protein, bovine serum
albumin [13]. The origin of the surface tension
increase is probably due to the fact that
the polymer does not bind to the surfactant
layer, and furthermore removes surfactant from
the surface to form bulk complexes in which the
polymer hydrophobic groups are less exposed to
water.
The surface tension of mixed solutions of poly-
mers and surfactants of the same charge is
slightly smaller than the surface tension of the
polymer-free surfactant solution. In this
case again, there is no binding of the surfactant to
the polymer, but an ionic polymer shifts the
critical micellar concentration (CMC) of the solu-
tions to lower values, exactly as a common salt
[11].
Fig. 1. Effect of PSS (x =45%) on C10E5 surface tension:
(open circles) C10E5; (closed circles) C10E5 +0.1% PSS; (trian-
gles) C10E5 +0.3% PSS. Data from [12].
192 A. Asnacios et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 189–197
Fig. 2. Effect of PAMPS(x=25%, Mw = 2.2× 106) on DTAB
surface tension: (open circles) DTAB; (diamonds) DTAB +75
ppm PAMPS; (crosses) DTAB +350ppm PAMPS; (closed
circles) DTAB + 750 ppm PAMPS. Data from [11].
3.2. Cationic surfactants
3.2.1. DTAB, CTAB and PAMPS
Mixed solutions of DTAB and AMPS show a
synergistic lowering of surface tension at very low
surfactant concentrations. As seen in Fig. 2, the
surface tension curve exhibits two break points:
the first one, known as the critical agregation
concentration (CAC), corresponds to the begin-
ning of the formation of a significant number of
polymer/surfactant complexes in the bulk. The
second one corresponds to the critical micellar
concentration (CMC). The surface tension does
not change if the polymer concentration is de-
creased down to very small values, below 100 ppm
[11] (Fig. 6). This remarkable result was also
found on polylysine-sodium dodecyl sulfate solu-
tions and explained with a simple model that we
will briefly recall below [14]. In our system we
have four kinds of ions, the polymer ions, P, the
surfactant ions, S, the sodium and bromide coun-
terions, Na+ and Br−. The Gibbs equation relat-
ing the surface tension variations, dg, to the
chemical potential variations, dmi, of the species i
present in the solution writes:
dg= − GNa + dmNa + −GBr − dmBr − − GPdmP − GSdmS
(1)
where Gi is the surface excess concentration of the
species i. If we now assume that the complex
formation at the surface is a cooperative phe-
nomenon and that the surfactant counterions are
replaced by the polymer charged units, the surfac-
tant and polymer counterions are released in the
bulk solution. It then follows that:
GNa+ = GBr − = 0 GS = xNGP (2)
because of electrical neutrality at the surface, N
being the number of monomers in the polymer
chain. Finally, since we deal here with dilute
solutions, dmi  kBT ln ci, kB being the Boltzmann
constant, T the absolute temperature and ci the
bulk concentration of species i, we get:
dg= − kTGsd ln (csc 1/xN) (3)
p
Because Nx, the number of charged monomers in
the polymer chain is a large number:
dg − kTGsd ln cs (4)
i.e. the surface tension is independent of the poly-
mer concentration. If we use this equation for the
data of Fig. 2, we find that around the CAC, the
area per surfactant molecule As at the surface is:
As = 1/Gs  789 5 A, 2
For a DTAB solution with a concentration close
to CMC, the area per molecule as calculated with
the Gibbs equation for charged monolayers dg=
− 2kTGsd ln cs is As  48 A, 2, i.e. significantly
smaller.
Fig. 3 shows the surface tension of mixed poly-
mer-surfactant solutions in the case of CTAB.
This surfactant has the same polar head as
DTAB, with its tail length longer by four CH2
groups. The general aspect of the curves of Figs. 2
and 3 is similar. The same synergistic lowering of
the surface tension at low surfactant concentra-
tions is observed. The surface tension plateau
after the CAC is 2 mN/m smaller for CTAB. As
the CMC, the CAC decreases with increasing
surfactant chain length. To be rigourous, we
should note that the second break point in Fig. 3
is not a CMC but rather a Krafft point, at the
temperature of our measurements. The main dif-
ference between the two surfactants is that the
CAC plateau stops before the CMC for DTAB
 A. Asnacios et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 189–197
and after for CTAB. In other words, the surface
tension of the polymer-DTAB mixtures is always
smaller than that of the pure DTAB solutions,
while the curve for polymer-CTAB mixtures and
that for CTAB alone, cross over around 0.5 mM
of surfactant. The behavior of CTAB is however
the most frequent in polymer-surfactants solu-
tions, where surface tension curves for polymer-
free and polymer-surfactant solutions cross
around the CMC of the surfactant [1]. In this
case, at surfactant concentrations higher than the
CMC, the addition of polyelectrolyte induces an
increase in the surface tension. This phenomenon
can be explained by the association of polymer
and surfactant in the bulk: if the bulk free surfac-
tant concentration is not sufficient, micelles can-
not be formed. In fact, it is interesting to note
that the maximum polyelectrolyte concentration
used in these measurements (750 ppm) corre-
sponds to 1.7 mM of charged monomers. This
concentration is lower than the CMC of DTAB,
but higher than that of CTAB. Thus, one can say,
that when the surfactant concentration equals the
CMC in polymer-CTAB mixtures, all the charged
sites of the polyelectrolytes are not bound to
surfactant molecules so the CTAB is still associat-
ing with the polymer in the bulk: it is worth
noting that the CAC plateau of the CTAB-poly-
mer system stops at about 2 mM of surfactant.
Fig. 3. Effect of PAMPS(x=25%, Mw = 2.2× 106) on CTAB
surface tension: (open circles) CTAB; (closed diamonds)
CTAB+ 750 ppm of polymer. Data from [15].
193
Fig. 4. Influence of the degree of charge of polyelectrolyte on
the PAMPS-DTAB solutions surface tension, (solid line)
DTAB; (dotted line) DTAB + 750 ppm of polymer x = 25%;
(closed circles) DTAB +750 ppm of polymer x =10%; (open
triangles) DTAB +75 ppm of polymer x= 10%. The area
noted ‘A’ corresponds to surfactant concentrations, where the
mixed solutions remain turbid for months, while the area ‘B’
corresponds to concentrations where the solutions become
clear after about a day. Data from [15].
We have found that the polymer molecular
weight does not have any measurable influence on
the surface tension, provided that the degree of
charge, x, is the same [15]. This is consistent with
the adsorption model recalled above, each surfac-
tant being complexed by a charged monomer.
When the degree of charge is increased, the sur-
face tension decreases. Fig. 4 shows the surface
tension for DTAB and PAMPS for which x=10
and 25%. For the smallest degree of charge, the
CAC is no longer well defined. One rather ob-
serves an inflection point around 1 mM of DTAB,
afterwhich the solutions become turbid. If we
apply Eq. (4) to evaluate the area per surfactant
molecule for x= 10% we find close to CAC:
As = 1/Gs  1009 5 A, 2
This area is larger than for x= 25% (78 A, 2). This
is probably associated to the fact that the polymer
at the surface acts as a spacer for the surfactant
molecules. Indeed, each charged polymer site be-
ing complexed with a surfactant molecule, the
distance between the molecules should increase if
the distance between the sites increases. However,
the variation in As is smaller than expected for a
194 A. Asnacios et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 189–197

completely flat adsorption of the polymer (the others are thicker and denser (larger refractive
area As should then increase by a factor 2.5, ratio index and thicknesses around 1000 A, ). These last
of the two x values). The polymer configuration domains are possibly microgels, precursors of the
near the surface is therefore, certainly different, precipitation in the bulk. These microgels have
and the thickness of the polymer layer, larger with also been observed in the foam films made from
the smaller degree of charge. This was investi- these solutions [16].
gated by ellipsometry measurements. In order to better locate the onset of associa-
Ellipsometry experiments allows the determina- tion in bulk, we have measured the bulk viscosity
tion of an ‘optical thickness’ (d) of the mixed of the solutions. The results are shown in Fig. 5.
monolayer, which is a rough average of the thick- The effect of surfactant addition on the bulk
ness of the zone where the surfactant and the polymer solutions is equivalent to salt addition
polymer are located. For DTAB before CAC, this below a concentration of about 0.7 mM. The salt
thickness d increases when the degree of charge screens the electrostatic repulsions, that swell the
decreases, from about 80 A, ( 940 A, ) for x= 25% polyelectrolyte molecules and reduces the dimen-
to about 200 A, ( 950 A, ) for x =10%. For a sions of the chains. Thus, the interactions between
polymer free DTAB solution just above CMC, macromolecules become weaker and the viscosity
d=10 A, . The thickness of the mixed layer is decreases. Above 0.7 mM DTAB, the reduction of
therefore, mainly the thickness of the polymer viscosity is larger with the surfactant than with
region. For x = 25%, the thickness is ten times the salt. This is due to the bulk complexation of
smaller than the gyration radius of the polymer
polymer and surfactant and to the precipitation of
molecules (as measured in a 0.1 M solution of
the complexes: the solutions become turbid, and
LiNO3). Therefore, the polymer probably
when all the polymer is precipitated, the solution
stretches out along the surface, allowing the com-
viscosity approaches that of water. This occurs
plexed surfactant molecules to have their hydro-
around a surfactant concentration of about 2 and
carbon chains in the air. The thickness can also be
9 mM, respectively, for degrees of charge x of 25
calculated using only one ellipsometric angle (for
and 10%. Clearly, the complexation occurs over a
thicknesses smaller than 100 A, , the other angle is
sharper concentration range for the largest degree
smaller than the instrumental accuracy) and the
area per molecule deduced from the adsorption
model. There is a good agreement between the
two determinations for x = 25%, but for x= 10%,
the d value obtained with the second method is
unrealistic (d = 238 A, ), outside of the error bar of
the direct determination. This might be due to the
fact that the validity of the adsorption model fails
when the degree of charge decreases. We will see
below that the cooperativity of the adsorption
and of the complexation in the bulk is less impor-
tant for the less charged polymer, and it is possi-
ble that some counterions are still present in the
surface layer. In the limiting case where, x= 0, we
expect no complexation at the surface at all, and
the model would then be completely
inappropriate.
The turbid solutions above CAC have non ho- Fig. 5. Comparison of the effect of added DTAB and salt on
the bulk viscosity of 750 ppm solutions of PAMPS: (closed
mogeneous interfaces. One observes two types of circles) x =25% and DTAB; (open circles) x =25% and KBr;
domains with macroscopic extensions: some are (closed diamonds) x =10% and DTAB; (open diamonds) x=
similar to the adsorbed layers before the CAC, the 10% and KBr. Data from [15].
 A. Asnacios et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 189–197 195

of charge: the complexation of a surfactant

molecule with a charged site of the polymer is
probably favoured by the presence of a second
nearby surfactant molecule. For the smallest de-
gree of charge, the distance between charged sites
is larger, and the cooperativity is thus reduced.
Note that for surfactant-free solutions, above 1
mM in KBr salt concentration, the electrostatic
interactions are sufficiently screened, and the solu-
tions with polymers of different degree of charge,
have the same viscosity.

3.2.2. DTAB-PSS
The behavior of mixed DTAB-PSS solutions is
very different from that of DTAB-PAMPS. We
will present here preliminary results obtained for
x =100% and Mw =70 000. Firstly, for given sur-
factant and polymer concentrations, the decrease
of surface tension is much smaller for PSS (Fig.
6). Secondly, there is no evidence of surface ten-
sion saturation above a certain polymer concen-
tration, and the CAC depends on polymer
concentration (Fig. 7). For a given surfactant
concentration, the surface tension decreases upon
addition of polymer and increases again after a
minimum close to the concentration at which the
bulk ionic concentrations of polymer and surfac-
Fig. 6. Surface tension of mixed DTAB-PAMPS (a) or PSS(b)
tant are equal. This indicates desorption of species solutions versus polymer concentration: (open circles) pure
present in the monolayer above this concentra- PAMPS and PSS; (closed circles) PSS + 10 − 4 M DTAB;
tion. Let us point out that a similar trend was (triangles) PAMPS + 0.5 ×10 − 4 M DTAB; (diamonds)
observed in the experiments of Buckingham et al. PAMPS+ 2 10 − 4M DTAB. Data from [21]. The lines are
guides to the eye.
[14]. Obviously, the simple adsorption model pre-
sented above fails and more work is needed to
clarify this complex surface behavior. It should be itation of the bulk complexes. It is to be noted
pointed out that contrary to the PAMPS poly- that polystyrene sulfonate does not precipitate in
mers studied, the fully sulfonated PSS is not monovalent salt solutions, but that trivalent salts
completely ionized in aqueous solutions, because are required for this purpose [18]. The surfactant
of Manning condensation of part of the counteri- used here is monovalent and the precipitation is
ons (spontaneous condensation allowing to reduce probably also induced by complexation of the
the electrostatic potential along the polymer hydrophobic parts of the polymer backbone with
chain, so that the chemical potential of free and the chains of the surfactant. The role of the
associated counterions could stay equal) [9,25]. backbone hydrophobicity of PSS in also impor-
The bulk behavior is however, similar for the tant in the formation of bulk complexes. [19]
two polymers as evidenced from viscosity mea-
surements [17]: the effect of the polymer is a 3.3. Connection with foam stability
simple salt effect below the CAC, and above
CAC, the viscosity decreases sharply towards the Foams made with DTAB solutions are very
water viscosity, this being accompanied by precip- unstable. Foam films made at concentrations
196 A. Asnacios et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 189–197
Fig. 7. Surface tension of mixed DTAB-PSS versus surfactant
concentration: (crosses) DTAB; (circles) DTAB + PSS 0.1%;
(squares) DTAB +PSS 0.2%; (triangles) DTAB + PSS 0.4%.
The lines are guides to the eye.
lower than CACs break instantaneously. When
small quantities of polymer are added, the foam
films become much more stable. Their drainage
can be studied by videointerferometry, and inter-
esting stratification processess have been evi-
denced [16,20,21]. Preliminary experiments of
surface compression viscoelasticity have shown
that the elasticity of mixed DTAB-PSS layers
increases with polymer concentration. Measure-
ments done at two very small DTAB concentra-
tions, where the pure DTAB solutions do not
show any measurable viscoelasticity [10], lead to
the elasticity values reported in Table 1. Small
amounts of PSS then produce a significant in-
crease of surface elasticity, even when the surface
tension is still close to that of water. This increase
in surface elasticity stabilizes the film against rup-
Table 1
Surface compression elasticity e for DTAB-PSS solutions mea-
sured at 800 Hz, for different surfactant and polymer concen-
trations cS and cP respectivelya
cs (mM) cp (ppm) g (mN/m) o (mN/m)
0.1 100 72 1 nisms are different below and above CAC: below
0.2 70 6 CAC, the stabilization is probably associated to
0.1 200 70 3
0.2 68 13
a
The surface tensions g are also given.
ture and might explain the enhancement of the
stability of the foam films [22]. Above CAC, the
drainage of the foam films is very different: mi-
crogel formation in the film is suggested by the
videointerferometry studies [16]. These observa-
tions are similar to others on mixed surfactant-
protein films [23]. In both cases, extremely stable
films are obtained, visibly associated to an immo-
bilization of the solubilized species in the gelified-
like film.
4. Summary and conclusion
The addition of polyelectrolytes to dilute sur-
factant solutions leads to extremely varied effects.
Nonionic surfactants can be depleted from the
surface by an hydrophobic polyelectrolyte such as
PSS. Ionic surfactants of opposite charge lead to
a synergistic surface tension lowering due to coad-
sorption of a non surface active polyanion and
oppositely charged surfactant ions. Viscosity mea-
surements reveal a difference in the polyelec-
trolyte-surfactant interaction in the bulk and at
the air/solution interface. While a highly surface-
active complex forms at the interface, there is no
significant binding between the two species in the
bulk at the very low surfactant concentrations
where the synergistic effect first takes place. For a
very hydrophilic polymer such as PAMPS, we
have found that the surfactant complex is rather
thin, suggesting that the polymer chains are
stretched out along the surface, probably dangling
into water between complexation sites, and that
the counterions are expelled in the bulk. The
cooperativity of the association decreases when
the degree of charge decreases. For the more
hydrophobic PSS, the association with surfactants
monolayers is clearly different and deserves to be
studied in more detail
The mixed layers of polymer and surfactant of
opposite charge enhance the stability of the foams
made from the solutions. The stabilization mecha-
the increase in surface viscoelasticity, whereas
above CAC, the stabilization is visibly associated
to the gel-like aspect of the foam films.
 A. Asnacios et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 167 (2000) 189–197
Other polyelectrolytes, more hydrophobic or
with larger persistence lengths are currently under
study to generalize these observations.
Acknowledgements
This work was supported in part by Institut
Français du Pétrole. Part of the results are already
published in the more detailed references
[11,12,15]. We are grateful to Ewa Radlinska for
allowing us to reproduce her surface tension data
in Fig. 1, to Francoise Lafuma for the synthesis of
the polymer used for the measurements of Fig. 1,
and to Jean-François Argillier for the samples of
PAMPS and the bulk viscosity measurements.
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