Colloids and Surfaces A: Physicochemical and Engineering Aspects, 16 (1993) 283-288 283

Elsevier Science Publishers B.V., Amsterdam

Segregation in aqueous systems of a polyelectrolyte and

an ionic surfactant

Kyrre Thalberg” and Bj6rn Lindmanb

“Pharmaceutical Department, Astra Draco AB, P.O. Box 34, S-221 00 Lund, Sweden
bDepartment of Physical Chemistry 1, Chemical Centre, Lund University, P.O. Box 124, S-221 00 Lund,
Sweden

(Received 9 November 1992; accepted 15 December 1992)

Abstract

Phase diagram studies have been carried out for systems of a polyelectrolyte and an oppositely charged surfactant in
the presence of high concentrations of salt, and for systems of a polyelectrolyte and a surfactant with the same charge.
All the systems studied display phase separation of the segregative type. In the former case, phase separation is
facilitated by increasing either the alkyl chain length of the surfactant or the molecular weight of the polyelectrolyte.
In the latter case, phase separation takes place in the absence of salt but is markedly enhanced by salt addition. An
increased surfactant chain length and an increased polyelectrolyte molecular weight facilitates phase separation also in
this case. For both types of system the tie lines are markedly skewed, an observation which cannot be explained by
Flory-Huggings-type models.

Keywords: Ionic surfactant; polyelectrolyte; phase diagrams; segregation.

Introduction The study of polymer-surfactant interactions is

a relatively young field of research, and until the
The study of phase behavior has a long history last few years, only a few phase diagram studies
within the field of surfactant science, and phase have been carried out. The field has been reviewed
diagrams are widely acknowledged as an appro- by Goddard [4] and the recent developments are
priate and fruitful way of representing binary sur- described by us in a book dedicated to the field of
factant-water systems as a function of temperature polymer-surfactant interactions [S]. For systems
as well as ternary systems of surfactant, water and of an ionic surfactant and an uncharged polymer,
a third component (oil, fatty acid or cosurfactant) phase separation does not normally occur; on the
at a given temperature (and pressure) [l]. contrary, an ionic surfactant may sometimes
Also for polymer systems, phase diagram studies increase the solubility of a non-ionic polymer [6].
have a long tradition, in particular for systems of For systems of a polyelectrolyte and a surfactant
two polymers in a common solvent [2]. In this of opposite charge, however, phase separation
case, theoretical modeling of the phase behavior seems to be the general case, and often leads to
based on the Flory-Huggins theory has been an precipitation of a polyelectrolyte-surfactant com-
important topic, especially for two uncharged poly- plex. In some early work, so-called “solubility
mers in a common solvent [3].
diagrams” were developed, showing the areas in

Correspondence to: K. Thalberg, Pharmaceutical Dept., Astra

the phase diagram where phase separation
Draco AB, P.O. Box 34, S-221 00 Lund, Sweden. occurred [7]. Such a diagram, however, does not

0927-7757/93/$06.00 0 1993 - Elsevier Science Publishers B.V. All rights reserved

284 K. Thalberg, B. LindmanlColloids Surfaces A: Physicochem. Eng. Aspects 76 (1993) 283-288

directly give the number or composition of the For oppositely charged systems, the influence of
separating phases. surfactant chain length and polyelectrolyte molecu-
More recently, the present authors worked out lar weight is studied. In view of the above results,
phase diagrams for systems of the anionic poly- it may be assumed that a segregative phase behav-
saccharide sodium hyaluronate and cationic surfac- vior will be observed also in systems with polyelec-
tants of the alkyltrimethylammonium bromide type trolyte and surfactant having the same charge. To
[&lo]. In these systems, phase separation results verify this, the system of sodium hyaluronate and
in the formation of two clear and isotropic phases sodium dodecyl sulfate (NaC,$) with and without
in equilibrium, and for each sample the composi- added salt was studied. The results of this study
tions of the two phases were determined. Phase have been presented in the above-mentioned review
separation was assessed to be of the associative paper on polymer-surfactant interactions [S] but
type, i.e. the polyelectrolyte and the surfactant will be discussed here in a more specific context.
separate out together, leaving behind a water-rich Very recently, a review article comparing the
“supernatant” phase, dilute in both polyelectrolyte phase behavior of polymer-polymer, polymersur-
and surfactant. As seen in the upper left phase factant and surfactant-surfactant systems has been
diagram in Fig. 1, a series of samples with increas- prepared [ 121. It is emphasized that the two former
ing total surfactant concentration typically traces types display very large similarities.
out a droplet-shaped two-phase region which is
anchored close to the water corner. The wide Experimental
general applicability of these findings was inferred
by the occurrence of the same type of phase Materials
behavior when hyaluronate was exchanged by
polyacrylate, and also in a system comprising the Sodium hyaluronate was provided by Kabi
cationic polymer poly(diallyldimethylammonium Pharmacia AB, Uppsala, Sweden. The molecular
chloride) (PDADMAC) and the anionic surfactant weight M, of the present sample used was 2.8 * 1O6
sodium octyl sulfate [I 11. as determined by low-angle laser light scattering
Interestingly, the observed phase behavior was (LALLS). The reduction of the molecular weight
highly sensitive to the addition of a simple salt was performed by acid hydrolysis with 0.1 M HCl
[lo]. This is illustrated in Fig. 1, where phase at 70°C followed by neutralization with NaOH
diagrams for the system of sodium hyaluronate and dialysis to remove the excess salt.
(NaHy) and tetradecyltrimethylammonium bro- Cationic surfactants of the alkyltrimethylam-
mide (C,,TAB) at various concentrations of added monium bromide type were purchased from Tokyo
NaBr are given. It can be seen that the area of the Kasei Inc., Japan. The surfactants will be denoted
twoophase region is markedly reduced already on C,TAB, where n is the number of carbon atoms in
the addition of 75 mM NaBr, and with 250 mM the alkyl chain. In this study, n ranges from 8 to
NaBr it has completely disappeared. At still higher 14. Sodium dodecyl sulfate (NaC,,S) was obtained
concentrations of NaBr, however, phase separation from B.D.H., UK, and NaBr, suprapur, was from
also occurs in the system, but it is of a different Merck, Germany.
type and results in one surfactant-rich and one
polymer-rich phase. This segregative type of phase Methods
behavior is analogous to that observed in polymer
systems, which is often referred to as polymer Phase diagrams have been established by the
incompatibility [2,3]. same method as described previously [S]. In brief,
This work focuses on segregative phase behavior samples containing 1.0 wt% of polyelectrolyte and
in systems of polyelectrolyte and ionic surfactant. a varying surfactant concentration are mixed thor-
K. Thalberg, B. LindmanlColloids Surfaces A: Physicochem. Eng. Aspects 76 (1993) 283-288 285

C14~~~ C14TA B

0 mM NaBr 75mM NaBr

C,eTAB

250 mM NaBr

NaHy
10 20 30 10 20 30
500mM NaBr 1.0 M NaBr

Fig. 1. Phase diagrams for the NaHy-C,,TAB-water system at different levels of added NaBr. The molecular weight of the hyaluronate
was about 2.4. IO’. (Copyright permission from Plenum Press Inc., New York.)

oughly and equilibrated for at least 1 week. If solvent, polyelectrolyte and oppositely charged sur-
phase separation has occurred, the two phases are factant are four-component systems [lo]. At the
separated carefully and their relative amounts are high concentrations of added salt used in this
assessed. One of the phases, normally the superna- work, the salt will be quite evenly distributed
tant phase, is then analyzed for its contents of between the two phases in equilibrium and the
bromide (by titration with Hg(NO,),), polyelectro- systems may then be adequately represented by
lyte (by optical rotation) and surfactant (by freeze- pseudo-three-component diagrams showing the
drying and analysis of the carbon and nitrogen surfactant, the polyelectrolyte salt and water.
contents of the dry powder). Systems with solvent, polyelectrolyte and surfac-
The systems containing cationic surfactant were tant with a similar charge, however, are true
studied at room temperature (22-25°C) and the three-component systems as long as there is only
systems containing NaC,,S were studied at 40°C one type of counterion present. The addition of
in order to avoid precipitation of the surfactant. salt turns these systems into four-component
It should be noted that aqueous systems of systems.
286 K. ThaIberg, B. Lindman/Colloids Surfnces A: Physicochem. Eng. Aspects 76 (1993) 283-288

Results and discussion surfactant. We have not determined the aggrega-

tion numbers of the micelles formed at a content
Polyelectrolyte and surfactant of opposite charge of 1.0 M NaBr, but it is known that salt addition
increases micellar size for longer chain surfactants
We take as a starting point the system [Il.
NaHy-C,,TAB in the presence of high concen- The increase in the CMC for a surfactant of
trations of NaBr. As discussed above, this system shorter alkyl chain is another effect that influences
displays a segregative type of phase separation at the phase diagram. The free surfactant unimers
a content of 500 mM of added NaBr, and segre- and their counterions can be expected to behave
gation is enhanced by a further increase in the as ordinary simple salts and will provide no driving
NaBr concentration (Fig. 1). It can be noted espe- force for the phase separation, implying that the
cially that the tie lines are strongly skewed, i.e. the onset of phase separation appears at a higher
polyelectrolyte-rich phase takes up much more surfactant concentration for a surfactant with a
water than the surfactant-rich phase. higher CMC. As the high salt concentration present
In Fig. 2, phase diagrams at a content of 1.0 M strongly depresses the CMC, this will only be a
NaBr are shown for NaHy, M, =90 000 and the secondary effect and can be estimated to be approx-
surfactants C,TAB, C,,TAB and C,,TAB (the imately 2 wt% and 0.3 wt% for &TAB and
C1,TAB system is included for comparison, C,,TAB, respectively, and to be negligible for
although the molecular weight of the hyaluronate C,,TAB and C,,TAB.
preparation used was slightly different in this case, Again we observe that (in all the systems) the tie
see below). The systems all display the same type lines are strongly biased, and the effect seems to
of segregative phase behavior and we see that the be more pronounced for a surfactant with a longer
tendency to phase-separate is strongly enhanced alkyl chain. The effect seems to be far too strong
by an increased surfactant chain length. This is to be accounted for by Flory-Huggins-type model-
mainly due to the larger micelles formed by surfac- ing. We have at present no explanation for this
tants with a longer hydrocarbon chain, thus reduc- finding.
ing the loss in entropy on separating out the The influence of the polymer molecular weight
is shown in Fig. 3. As expected, phase separation

---NaHy
%NaHy - 10 20 30 40 50
% NaHy -
Fig. 2. Phase diagrams for various NaHy-C,TAB systems in
the presence of 1.0 A4 NaBr. Some tie lines are indicated with Fig. 3. Phase diagram for the NaHy-C,,TAB system in the
dotted lines. The hyaluronate molecular weight was about presence of 1.0 M NaBr at two different molecular weights of
9.0. 104, except for C,,TAB, where it was 2.4. 105. the hyaluronate.
K. Thalberg, B. LindmanlColloids Surfaces A: Physicochem. Eng. Aspects 76 (1993) 283-288 287

is enhanced by an increased molecular weight, just SDS

as expected from theory. However, the effect is not
very strong in view of the 30-fold difference in
molecular weight. A slight change in the direction
of the tie lines can be identified, i.e. the high
molecular weight hyaluronate displays a still higher
degree of skewness.
For the NaHy-C&TAB system, the possibility
of an increased surfactant concentration in the
polymer-rich phase with increasing polymer con-
centration and eventually a closing of the two-
phase area was discussed [lo]. Such behavior was
supported by a Flory-Huggins type modeling of % NaHy -
the system, from which closed two-phase regions
Fig. 4. Phase diagrams for the NaHy-NaC,,S system at 40°C
resulted. The design of our experimental method, without added salt and in the presence of 1.0 M NaBr.
however, makes a precise determination of the (Copyright permission from CRC Press, Boca Raton, FL.)
surfactant concentration in the polymer-rich phase
difficult for two reasons: firstly, this phase has a be suppressed by the addition of salt. As can be
very low volume fraction, and secondly, the calcula- seen, 1.0 M NaBr strongly facilitates phase separa-
tion involves the difference between two very large tion and furthermore induces a marked skewness
numbers since the surfactant analysis is carried out in the direction of the tie lines, which is even more
in the surfactant-rich phase. pronounced than for the above systems with oppo-
In order to investigate this behavior further, the sitely charged polyelectrolyte and surfactant. (The
dye powder Orange OT was dissolved in the molecular weight of hyaluronate was 90000.) The
equilibrium two-phase samples. A vague coloration phase behavior was also investigated in the pres-
was observed also in the polymer-rich lower phase, ence of 0.1 M NaBr. Interestingly, this salt level
indicating the existence of surfactant micelles in leads to only a slight effect in comparison with the
this phase. No clear trend of an increased surfactant salt-free system.
concentration in the polymer-rich phase at higher It must be noted that addition of salt also gives
surfactant concentrations could, however, be estab- additional effects, i.e. the size of the surfactant
lished in any of the systems studied. aggregates tends to increase and the interaction
parameters between the surfactant micelles and
Polyelectrolyte and surfactant of similar charge between the polyelectrolyte chains will be altered.
The growth of the micelles may be quite pro-
For systems comprising a surfactant and a poly- nounced when the surfactant is close to its Krafft
electrolyte with the same charge, it may be expected temperature, which is the case for NaC,,S in 1.0 M
that segregation will take place also in the absence NaBr. It is thus likely that the strong effect
of added salt. This is indeed observed in the NaHy observed at a content of 1.0 M NaBr is mainly due
and NaC,,S system (Fig. 4), but the two-phase to an increase in the aggregation number of the
region appears at relatively high surfactant and surfactant micelles.
polyelectrolyte concentrations. This resistance to
segregation can be attributed to the substantial Conclusions
entropy loss of the surfactant and polyelectrolyte
counterions accompanying the phase separation, It may be concluded that polyelectrolyte-ionic
due to differences in charge density. The effect can surfactant systems may display a segregative type
288 K. Thalberg, B. LindmanlColloids Surfaces A: Physicochem. Eng. Aspects 76 (1993) 283-288

of phase behavior (a) when the surfactant and the with the figures. A grant from NUTEK (The
polyelectrolyte have similar charge; or (b) when National Board for Industrial and Technical
they are of opposite charge and a large amount of Development) is gratefully acknowledged.
salt is added. In both cases, the effects of surfactant
chain length, polyelectrolyte molecular weight and
(further) added salt are as expected, i.e. similar to References
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rather to be due to the properties of the surfactants, actions-recent developments, in E.D. Goddard and K.P.
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Acknowledgments

We thank Svante Nilsson and Lennart Piculell

for fruitful discussions and Ingegerd Lind for help