J. Phys. Chem.

B 1998, 102, 7099-7105 7099

Mixed Solutions of Surfactant and Hydrophobically Modified Polymer. Controlling

Viscosity with Micellar Size

Susanne Nilsson,*,† Krister Thuresson,† Per Hansson,‡ and Bjo1 rn Lindman†

Physical Chemistry 1, Center for Chemistry and Chemical Engineering, Lund UniVersity, P.O. Box 124,
S-221 00 Lund, Sweden, and Department of Physical Chemistry, Uppsala UniVersity, P.O. Box 532,
S-751 21 Uppsala, Sweden
ReceiVed: February 22, 1998; In Final Form: June 3, 1998

The viscosity of mixtures of a hydrophobically modified cellulose polymer (HMHEC) and surfactants in
aqueous solution was determined as a function of the concentration of mixed micelles. It was shown that, in
solutions of low viscosity where the ratio between polymer hydrophobic tails and mixed micelles is low, a
high viscosity can be recovered by increasing the surfactant aggregation number in the mixed micelles. The
surfactant aggregation number of the mixed micelles was increased by adding either a screening electrolyte
or an oppositely charged surfactant to solutions containing the hydrophobically modified polymer and an
ionic surfactant. Time-resolved fluorescence quenching (TRFQ) was used to investigate the size of the mixed
micelles.

Introduction micelles in the present system. Addition of an oppositely

Solutions of hydrophobically modified water-soluble poly-
mers and surfactants have been widely investigated during the
past decade. A reason for this is their frequent use as rheology
modifiers.1-3 One class of such polymers consists of a (nonionic
or ionic) water-soluble backbone onto which a low amount of
hydrophobic side chains has been grafted.4-6 In dilute solutions
the hydrophobic tails associate intramolecularly to minimize
their water contact. In semidilute solutions intermolecular
association also takes place which macroscopically results in
an enhanced viscosity. It is well-known that the viscosity of
semidilute solutions of associative polymers is sensitive to the
presence of surfactants.1 Surfactant molecules are regarded to
influence the cross-linking between different polymer chains
due to the formation of mixed micelles composed of polymer
hydrophobic tails and surfactant molecules.
Several investigations have shown that the molar ratio
between the hydrophobic polymer tails and the mixed micelles
in which they participate is an important parameter for
determining the rheological response of the solution.7-10 Typi-
cally, a low viscosity follows from a decreased connectivity
between different polymer chains when the ratio becomes small.
This may cause difficulties in applications such as water-based
paint formulations where different kinds of surfactants are used
for other purposes such as to stabilize pigments, latex particles,
and fillers. This serves as the base for the present investigation
where the surfactant aggregation number of the mixed micelles
has been changed in a controlled way while monitoring the
viscosity. As a model system we have chosen aqueous solutions
of the nonionic polymer hydrophobically modified (hydroxy-
ethyl)cellulose (HMHEC) and the anionic surfactant sodium
dodecyl sulfate (SDS), which is a system well-known from
literature.11-16 Pure SDS micelles grow when a screening
electrolyte is added.17 A similar effect is expected for the mixed
† drying, the polymer was stored in a desiccator.
Lund University.
‡Uppsala University.
* To whom correspondence should be addressed.
S1089-5647(98)01237-1 CCC: $15.00 © 1998 American Chemical Society
Published on Web 08/21/1998
charged surfactant is known to increase the aggregation number
of ionic micelles,18,19 and this was another method employed
to control the size of the mixed micelles. Time-resolved
fluorescence quenching (TRFQ) was used to follow the changes
in the concentration of the mixed micelles as a function of
screening electrolyte concentration or as a function of the
fraction of cationic surfactant, while keeping the total surfactant
concentration constant. Furthermore, the viscosity was obtained
from oscillatory shear experiments and correlated to the
concentration of mixed micelles.
Experimental Section
Materials. Hydrophobically modified (hydroxyethyl)cellu-
lose (HMHEC) with the commercial name Natrosol Plus grade
330 was obtained from Aqualon. According to the manufac-
turer, HMHEC has a molecular mass of 250 000 and carries
grafted C16 alkyl chains corresponding to a hydrophobic
modification degree of 0.5-1 w/w %. The degree of substitu-
tion of hydroxyethyl groups per repeating anhydroglucose unit
of the polymer equals 3.3. In the present investigation the
polymer material was analyzed according to a description by
Landoll4 and found to contain 1.2 w/w % of C16 alkyl chains
of the (total) dry sample weight. This corresponds to 0.54 mm
alkyl chains in a 1 w/w % aqueous polymer solution. Using
the hydroxyethyl substitution degree as given by the manufac-
turer, 1.7 mol % of the anhydroglucose units contain alkyl
chains. Prior to use HMHEC was extensively washed with
acetone to remove unreacted alkyl chains, dried, dissolved in
water to a concentration of 1 w/w %, and centrifuged at 10 000g
to get rid of high molecular weight impurities (such as unreacted
cellulose). Low molecular weight impurities (such as salt) were
removed by dialysis against Millipore water in a Filtron
Ultrasette device. The dialysis was performed until the expelled
water showed a conductivity of less than 2 µS/cm. After freeze-
Sodium dodecyl sulfate (SDS) (specially pure) from BDH,
dodecyl trimethylammonium chloride (DoTAC) from TCI
7100 J. Phys. Chem. B, Vol. 102, No. 37, 1998
Tokyo Kasei, and sodium chloride (NaCl), ACS reagent, from
Sigma were used as supplied. Pyrene from Aldrich was
recrystallized twice from ethanol. N-Dodecylpyridinium chlo-
ride (DoPC) from Aldrich was recrystallized several times from
acetone. N-Cetylpyridinium chloride (CPC) (analytic grade)
from Merck was used as supplied.
Methods. Sample Preparation. The samples were prepared
from stock solutions by weight. All of them had a polymer
concentration of 1 w/w % (1 g of polymer per 100 g of solvent),
which is in the semidilute region and well above the critical
polymer concentration (ca. 0.2%) where intermolecular hydro-
phobic associations take place.11 The test tubes were of glass
and sealed with Teflon-tightened screw caps. The samples were
mixed by tilting the test tubes end over end several days at 25
°C. To prepare the samples for the TRFQ measurements which
all contained the water-insoluble pyrene, an accurate amount
of pyrene dissolved in ethanol was transferred to a beaker.
Finally, after evaporating off the ethanol, proper amounts of
HMHEC and Millipore quality water were added. All TRFQ
samples contained 10 µm pyrene. The concentration of pyrene
was chosen such that it was high enough to decrease the
influence of fluorescent impurities originating from the polymer
material but still small enough not to disturb the micelles. CPC
was used as a quencher in systems containing DoTAC or NaCl
since the long aliphatic chain of the cationic CPC implies a
strong binding also to cationic micelles. On the other hand,
DoPC was used in the reference system (HMHEC + SDS) in
order not to affect the aggregation number at low surfactant
concentrations.
Viscosity. The viscosity measurements were performed in
the oscillatory mode with a Carri-Med controlled stressed CSL
100 rheometer, which has an automatic gap setting. Two
different cone and plate geometries, 4 and 6 cm in diameter,
were used for high viscous and low viscous samples, respec-
tively. All measurements were carried out at 25 °C, and the
complex viscosity, η*, was calculated through
η* ) [(G′2 + G′′2)/(2πf)2]1/2 (1)
where G′ is the storage modulus, G′′ the loss modulus, and f
the frequency. In most samples the reported value corresponds
to the Newtonian plateau. However, in samples with high
viscosity sometimes this limit was not reached, and therefore
the viscosity is given at the lowest frequency measured (typically
0.005-0.01 Hz). This procedure results in slightly too low
absolute values in samples with high viscosity, while the general
trends remain unchanged.
Fluorescence Quenching (TRFQ). Time-resolved fluores-
cence decay data were collected with the single-photon counting
technique. A detailed description of the experimental technique
and equipment is given by Almgren et al.20 The fluorescence
from the probe (pyrene) was monitored at 395 nm following
excitation at 320 nm. All measurements were carried out at 25
°C. From experiments using quenchers (DoPC or CPC), the
concentration of hydrophobic domains, [M], was obtained from
the estimated average number of quenchers per micelle (hy-
drophobic domain), 〈n〉, using
M ) Qm/〈n〉 (2)
Qm is the concentration of quencher (DoPC or CPC) in the
micelles. All quenchers are assumed to be inside the micelles
as long as there is surfactant present. CPC distributes to the
micelles due to strong hydrophobic attractions, while DoPC was
used in mixtures with SDS where the free concentration of both
Nilsson et al.
cationic and anionic surfactants is expected to be very low. For
the pure HMHEC sample the free concentration of quencher
may become important (see below).
Infelta21 proposed the following function describing the time
evolution of the fluorescence signal, F(t), from a probe situated
in small uniform micelles in the presence of quenchers.
F(t) ) A1 exp[-A2t + A3{exp(-A4t) - 1}] (3)
A1 is the amplitude of the decay curve at the excitation event (t
) 0). In the case of stationary probe and quencher, i.e., when
both compounds reside in the micelles considerably longer than
the fluorescence lifetime of the probe (τ0), the other parameters
can be interpreted as22 A2 ) 1/τ0, A3 ) 〈n〉, and A4 ) kq, where
〈n〉 is the average number of quencher per micelle and xkq is
the deactivation rate in micelles containing x quenchers.
For every sample, two different fluorescence decay curves
were recorded, one without quencher which by fitting a single-
exponential function to the decay curve gave the fluorescence
lifetime of pyrene, τ0. The other decay curve, with quencher
present, is fitted with eq 3.
In one sample (1 w/w % HMHEC, with DoTAC to SDS
molar fraction of r ) 0.25) with large nonuniform aggregates
(as compared to the small micelles in the other samples), eq 3
resulted in poor fits. This is expected since it describes (in an
approximate way) the quenching in small micelles. Instead 〈n〉
was evaluated graphically by plotting the logarithm of the
relative fluorescence intensity against time for the quenched
sample.23 An extrapolation of the single-exponential part of
the quenched curve to time zero gives 〈n〉 as the difference in
the amplitude between the extrapolated (linear) curve and the
amplitude of the quenched curve. In principle, this method can
be used once it has been confirmed that the micelles are discrete;
i.e., the decay rate at long times is the same for the quenched
and for the unquenched samples. Note that 〈n〉 depends on the
distribution of the quencher between water and micelles, not
on the quenching process.
Results and Discussion
General Discussion. We start this section with a short review
of recent results from the literature in order to facilitate the
interpretation of our data. It is generally found that the viscosity
of a polymer solution increases strongly on hydrophobic
modification provided the concentration is high enough to allow
interpolymeric associations. However, this is only true within
certain limits. Of course, the modification degree must exceed
a certain threshold value; i.e., each polymer chain must contain
at least two hydrophobic tails on average to have the possibility
to form networks. Furthermore, Annable et al. showed that the
length of the hydrophobic tail must exceed ca. 6 carbons to
influence the viscosity in a solution of end-capped PEG
polymers.24 It is known that there is also an upper limit in
hydrophobic modification degree. A too high modification
degree and/or too long hydrophobic tails will result in dissolution
problems of the polymer material.16
Hydrophobic molecules tend to dissolve in the polymer
hydrophobic domains. Especially surfactants are expected to
bind to these regions.9 Typically the viscosity of a semidilute
polymer solution of constant concentration is expected to first
increase and then decrease as a function of added surfactant.
The increase has been attributed to two effects. An addition of
surfactant at low concentrations can be expected to increase both
the strength of the connections and the concentration of mixed
micelles. We refer the increased strength of the connections to
Solutions of Surfactant and Modified Polymer J. Phys. Chem. B, Vol. 102, No. 37, 1998 7101

an improved packing of surfactant molecules in the mixed

micellar corona. Such an improvement of the interface between
the micellar core and the aqueous environment is expected to
increase the residence time of the polymer hydrophobic tails in
the micelles (see below). An increased concentration of mixed
micelles is expected to cause a reorganization of polymer chains
from intra- to interaggregates.25 Thus, the number of polymer
strands that actually connects two mixed micelles and therefore
participate in the network increases. The decrease in viscosity
is generally regarded to be due to an untying process in which
the connections between different polymer chains are broken
when the concentration of mixed micelles become larger, and
the average number of polymer hydrophobic tails in each micelle
decreases.26 A general finding in an investigation by Piculell
et al.26 was that the breakdown of the network was strongly
correlated to a cooperative aggregation process of the surfactant
molecules.
In this context it may also be valuable to discuss the binding
of SDS to hydrophobically modified ethyl(hydroxyethyl)- Figure 1. Complex viscosity (filled circles) and concentration of
cellulose (HMEHEC), which is a cellulose derivative related micelles (open circles) as a function of SDS concentration in a 1 w/w
to HMHEC. We start to discuss the unmodified parent polymer % HMHEC solution. The lines only serve as a guide to the eye.
(EHEC) which also interacts with SDS and promotes aggrega-
tion of the surfactant. At the critical aggregation concentration Before proceeding, we note that the concentration of micelles
(cac) rather well-defined aggregates are regarded to form, and estimated from TRFQ in Figure 1 relies on the assumption that
all quenchers (DoPC) are distributed in the micelles. As long
typically the aggregation number is smaller than in normal
as there are SDS bound to the micelles, the error will be
micelles (20-40 as compared to 60).9,27-30 The hydrophobic
negligible due to the favorable electrostatic interactions. In fact,
modification of HMEHEC provides nucleation sites at which
a comparison of the estimates in the presence and in the absence
individual surfactant molecules can bind. Thuresson et al.
of SDS (see Table 1) suggests that the concentration of free
showed that the binding of SDS to HMEHEC could be divided
quencher is small also in the latter case.
into two regions.9,31 At low concentrations the binding was
It is important to point out that the concentration of micelles
reminiscent of the adsorption to a hydrophobic macroscopic
as calculated from 〈n〉 is independent of the SDS binding. In
surface, and the binding could be described with a Langmuir
contrast, to obtain the number of SDS per aggregate, Nagg, we
adsorption isotherm. Therefore, at low concentrations a constant
need to know the binding isotherm. However, even with the
fraction (in this particular case about 0.5) of the added surfactant
isotherm at hand the binding at low SDS concentrations would
material binds to the hydrophobic moieties. On increasing the
be different in the presence of the quencher. Nevertheless, by
surfactant concentration the sites available for noncooperative
keeping in mind the qualitative nature of the result, we find it
binding become saturated, and the fraction of bound SDS
is instructive to calculate the aggregation number assuming that
decreases. When the free SDS concentration in the HMEHEC
the binding isotherm is the same as reported for HMEHEC/
solution corresponds to the cac in the EHEC solution (3.5 mm),
SDS (see above),9 except that the cac is 6 mm (instead of 3.5
the isotherm is determined by a cooperative process, and
mm). The results for low and high SDS concentrations are given
aggregates resembling those in the EHEC solution form.
in Table 2. At intermediate concentrations no calculation was
HMHEC and SDS. The main purpose of the present study made due to uncertainties in the binding isotherm. The small
is to investigate the effect of salt and an oppositely charged aggregation numbers found at low SDS concentrations are in
cosurfactant on HMHEC-SDS mixtures. However, we start agreement with a noncooperative binding to aggregates formed
with a characterization of the system in the absence of additives. by the polymer side chains. Note that, on a qualitative level,
Figure 1 shows how the viscosity changes with the SDS the same conclusion can be made even if all SDS is bound to
concentration in 1 w/w % HMHEC solutions. The pronounced the aggregates (multiply the aggregation numbers by two). The
viscosity maximum at 7 mm SDS is in good agreement with values obtained above 10 mm SDS agree very well with those
the result by Tanaka et al.12 The estimated concentration of reported in the HMEHEC/SDS system. In this range the
micelles (from TRFQ) is also presented in Figure 1. The nearly influence of the quencher on both the binding and the aggrega-
constant concentration of micelles to the left of the viscosity tion number is expected to be small.33
maximum confirms the existence of aggregated polymer side The TRFQ measurements also provide information about the
chains already in the absence of surfactant, as previously dynamics of the quenching process. Here, kq, the quenching
observed with HMEHEC. In further agreement with the latter frequency within the micelles, is sensitive to the size and the
system, the reduction of the viscosity at higher surfactant microviscosity of the micelles. In polymer/surfactant com-
concentrations can be explained by an increased micelle plexes, kq, which is independent of 〈n〉 , is generally found to
concentration as the cac in the corresponding unmodified system be smaller than in the corresponding pure surfactant micelles
is exceeded. In the present system the cac is about 6 mM as even when the former aggregates are smaller.34 This effect,
indicated by a significant drop in the viscosity observed in dilute which is present also in HMHEC-SDS (Table 1), has been
HEC solutions.32 This value is higher than for the more attributed to a decreased mobility within the polymer-surfactant
hydrophobic EHEC, where a stronger interaction with the complexes.35 The most striking observation in the present
polymer is at hand. However, for both polymers, the maximum system is, however, the slow quenching in the polymer-
in viscosity in the modified system is positioned close to the dominated aggregates. In fact, there seems to be a turn over to
cac in the unmodified system. faster quenching rates at the onset of the cooperative binding
7102 J. Phys. Chem. B, Vol. 102, No. 37, 1998 Nilsson et al.

TABLE 1: Parameters Estimated from TRFQ Measurements on Mixtures of HMHEC-SDS, HMHEC-SDS-NaCl, and
HMHEC-SDS-DoTAC
sample quencher/mm τ0/ns kq × 10-7/s-1 χ2 a 〈n〉 [M]/mm
1 w/w % HMHEC; DoPC
0 mm SDS 0.1 246 0.53 1.14 1.17 0.085
0.2 mm SDS 0.1 243 0.61 0.989 0.989 0.101
1.0 mm SDS 0.1 255 0.79 1.08 0.728 0.137
5.0 mm SDS 0.1 233 1.4 1.31 1.05 0.095
7.0 mm SDS 0.2 222 1.5 1.02 1.24 0.162
8.0 mm SDS 0.2 221 1.7 0.950 1.39 0.144
9.0 mm SDS 0.2 225 1.7 1.03 1.28 0.156
11.9 mm SDS 0.2 218 1.8 1.07 1.01 0.198
17.9 mm SDS 0.2 215 1.9 1.01 0.658 0.304
1 w/w % HMHEC + 15 mm SDS; CPC
0 M NaCl 0.2 214 2.1 1.00 0.789 0.254
0.03 M NaCl 0.2 205 1.9 0.852 0.920 0.217
0.05 M NaCl 0.2 204 1.9 1.14 0.982 0.204
0.1 M NaCl 0.2 200 1.7 1.08 1.08 0.186
0.2 M NaCl 0.2 201 1.7 1.01 1.20 0.166
0.4 M NaCl 0.2 202 1.6 1.09 1.36 0.148
0.5 M NaCl 0.2 203 1.5 1.09 1.41 0.142
1 w/w % HMHEC + 30 mm (SDS + DoTAC); CPC
0 DoTAC molar ratio 0.5 217 2.3 1.08 0.889 0.562
0.10 DoTAC molar ratio 0.5 207 1.4 1.17 1.61 0.311
0.20 DoTAC molar ratio 0.5 189 0.67 1.68 3.18 0.157
0.25 DoTAC molar ratio 0.5 178 0.45 3.25 4.35b 0.115
0.90 DoTAC molar ratio 0.5 177 1.6 1.07 3.54 0.141
1.0 DoTAC molar ratio 0.5 191 4.4 1.19 1.69 0.296
a Quality of fit. b Graphical evaluation gives 〈n〉 ) 4.55 and [M] ) 0.110.

TABLE 2: Calculated Surfactant Aggregation Numbers and unexpected because on addition of simple salt the relative
the Number of Polymer Hydrophobic Tails per Mixed reduction of the cac (for ionic surfactants) has been found to
Micelle for the HMHEC-SDS, HMHEC-SDS-NaCl, and
HMHEC-SDS-DoTAC Systemsa resemble that for the reduction of cmc.36,37 Thus, the concentra-
tion of free surfactant required to achieve cooperative surfactant
sample cac/mM Nagg,s nb binding can be expected to decrease substantially, and the
1 w/w % HMHEC viscosity maximum could be expected to be located at a lower
0 mm SDS 0 6.4 total SDS concentration than in the salt-free system. However,
0.2 mm SDS 1 5.3
1.0 mm SDS 4 3.9
except from a decreased cac,38 micellar growth is also promoted
5.0 mmSDS 5.7 by the reduced electrostatic repulsion between the charged
7.0 mm SDS 6 6 3.3 surfactant headgroups which follows from salt addition.39 From
8.0 mm SDS 6 14 3.8 the viscosity profile’s point of view, this is expected to oppose
9.0 mm SDS 6 19 3.5 the effect of a decreased cac and can therefore be the explanation
11.9 mm SDS 6 30 2.7
17.9 mm SDS 6 39 1.8
for the observation by Tanaka et al.12 Indeed, in the present
investigation the surfactant aggregation number Nagg of the
1 w/w % HMHEC + 15 mm SDS
mixed micelles was found to increase with increasing NaCl
0 M NaCl 6 35 2.1
0.03 M NaCl 2.3 58 2.5 concentration in a system composed of 15 mm SDS and 1 w/w
0.05 M NaCl 1.6 65 2.6 % HMHEC; see Table 2. As suggested by data in the literature,
0.1 M NaCl 0.97 75 2.9 it was assumed that salt induces the same relative reduction of
0.2 M NaCl 0.67 86 3.3 the cac as that of the cmc.37,40 This is expected to be a good
0.4 M NaCl 0.44 98 3.6
assumption at the present SDS concentration where the effect
0.5 M NaCl 0.40 103 3.8
of the hydrophobic modification of the polymer on the micelles
1 w/w % HMHEC + 30 mm (SDS + DoTAC) is negligible.
0 DoTAC molar ratio 6 43 1.0
0.10 DoTAC molar ratio 0 96 1.7 Throughout this section the polymer and surfactant concen-
0.20 DoTAC molar ratio 0 191 3.4 trations were kept constant at 1 w/w % and 15 mm, respectively,
0.25 DoTAC molar ratio 0 261 4.7 and we report on variations in the viscosity and changes in the
0.90 DoTAC molar ratio 0 213 3.8
concentration of mixed micelles as a function of NaCl. In
1.0 DoTAC molar ratio 19 37 1.8
Figure 2 it can be seen that the viscosity increases with added
a Note that the cac values used in the calculations are estimated (see
NaCl up to a concentration of 0.1 M. At higher NaCl
text). b Number of polymer hydrophobic tails per hydrophobic domain. concentrations the viscosity decreases. In contrast, it was found
that the concentration of mixed micelles continuously decreased
(i.e., surfactant-dominated aggregates). This behavior, which with salt. The fastest decrease was observed at low NaCl
was also found in HMEHEC/SDS,9 points to the difference in concentrations. One explanation for the decrease in viscosity
the nature of the two types of aggregates. at high NaCl concentrations could be a too low concentration
Effect of Salt. In an investigation regarding the HMHEC- of mixed micelles which opposes a fully developed network
SDS system, Tanaka et al.12 found that NaCl only had a minor due to intraaggregation of the polymer chains. However, this
effect on the viscosity profile as a function of SDS in a solution explanation seems less likely because a high viscosity could
containing 1 w/w % HMHEC. At first this is somewhat not be recovered by increasing the SDS concentration above
Solutions of Surfactant and Modified Polymer
Figure 2. Complex viscosity (filled circles) and concentration of
micelles (open circles) versus the concentration of NaCl in samples
with 1 w/w % HMHEC and 15 mm SDS. The lines are drawn to guide
the eye.
Figure 3. Complex viscosity in mixtures of 1 w/w % HMHEC, SDS
and NaCl.
Figure 4. Phase boundaries for the mixed cationic-anionic surfactant
system at different molar fractions of DoTAC at a total SDS + DoTAC
concentration of 30 mm.
15 mm while keeping the NaCl concentration constant (corre-
sponding to an increase in the concentration of mixed micelles)
(Figure 3). Furthermore, as mentioned above, Figure 1 indicates
that the increase in viscosity on addition of SDS is not due to
an increased concentration of mixed micelles. The same data
plotted in a different way (see Figure 6) show that the viscosity
increases abruptly with the concentration of mixed micelles in
the HMHEC-SDS system. This behavior is not reproduced
by the corresponding curve (viscosity as a function of concen-
tration of mixed micelles) for the system where the NaCl
J. Phys. Chem. B, Vol. 102, No. 37, 1998 7103
Figure 5. Complex viscosity (filled circles) and concentration of
micelles (open circles) versus the molar fraction of DoTAC at the total
DoTAC + SDS concentration of 30 mm in a 1 w/w % HMHEC
solution. Note the phase separation area at intermediate ratios. The lines
only serve as a guidance for the eye.
Figure 6. Complex viscosity as a function of the concentration of
micelles for three different systems. (A) 1 w/w % HMHEC + SDS.
The changes with the SDS concentration (from left to right 0, 3, 5, 6,
6.5, 7, 7.6, 8, 9, 11, 15, 30, 50 mm) are depicted with triangles. (B) 1
w/w % HMHEC + 30 mm surfactant (SDS + DoTAC). Circles mark
the variation with DoTAC to total surfactant molar fraction (r ) 0,
0.05, 0.10, 0.15, 0.20, 0.25, 0.28, 0.30, 0.90, 1.0). The hatched lines
depict the phase separation area; the line is only drawn to make it easier
to follow the trend curve. (C) 1 w/w % HMHEC + 15 mm SDS +
NaCl. The variation with the NaCl concentration (0, 0.03, 0.05, 0.10,
0.20, 0.40, 0.50 M) is marked with filled diamonds. In samples where
the viscosity was measured at a concentration intermediate to two
concentrations at which TRFQ measurements were performed; the
concentration of micelles, [M], was extrapolated.
concentration was changed (polymer and SDS concentrations
kept constant). Here the variations were found to be more
gradual. This points to a different mechanism (than stoichi-
ometry) at high NaCl concentrations.
We suggest that the decrease in viscosity at high concentra-
tions of a screening electrolyte is due to attractive forces within
the polymer-surfactant complexes which leads to a contraction.
In line with this we found that on further addition of NaCl an
associative phase separation occurred (at ca. 0.7-0.8 M NaCl).
7104 J. Phys. Chem. B, Vol. 102, No. 37, 1998
Thus, the solubility of the complex (and therefore the viscosity
of the solution) is determined by an interplay between electro-
static repulsion and an attraction due to a hydrophobic effect.
To summarize, as the system becomes microheterogeneous close
to the phase separation limit, the viscosity decreases.
Mixtures of Oppositely Charged Surfactants. Investiga-
tions concerning the phase behavior of mixtures of the oppositely
charged surfactants dodecyl trimethylammonium bromide
(DoTAB) and SDS have been reported by several authors.18,41,42
Techniques such as TRFQ, cryo-transmission electron micros-
copy (cryo-TEM), light scattering, and conductivity were used.
It was found that at a total surfactant concentration of 50 mM
a demixing with precipitation occurred in the interval r )
[DoTAB]/([SDS] + [DoTAB]) ) 0.38-0.88.41 Close to phase
separation (from r ) 0.30-0.38) the solution was found to be
slightly bluish and to contain larger aggregates, such as vesicles
and threadlike micelles, probably in equilibrium with smaller
micelles. Further away from the region of demixing the solution
was isotropic and contained only spherical micelles.
In the present investigation we have used a slightly different
system where the cationic surfactant has Cl- as the counterion.
The phase behavior at a total surfactant concentration of 30 mm
(DoTAC + SDS) is presented in Figure 4. In qualitative
agreement with the DoTAB-SDS system a turbid, bluish,
viscoelastic solution was observed at mixing ratios between r
) 0.32 and r ) 0.38, and the precipitation region extends from
r ) 0.38 to r ) 0.93.
To the mixtures of DoTAC-SDS was added HMHEC in a
concentration of 1 w/w %. It was found that the phase
boundaries were slightly changed. The “turbidity boundary”
moved from r ) 0.32 to r ) 0.30. On the DoTAC-rich side
the precipitation region was decreased from r ) 0.93 to below
r ) 0.90. At this stage we cannot decide whether this is a real
effect or the shift mainly is due to slow kinetics. However, no
phase separation was observed in any sample that was experi-
mentally investigated by TRFQ or rheology. Another specula-
tion is that anionic surfactants bind stronger to HMHEC than
cationic ones which also may have influence on the phase
behavior.
In qualitative agreement with the results obtained in the
HMHEC-SDS system on addition of NaCl, it was found that
the viscosity increased on addition of the cationic surfactant to
the HMHEC-SDS solution. The viscosity increase was cor-
related with a decreased concentration of mixed micelles (Figure
5). At a molar fraction of r ) 0.18, the viscosity exhibits a
sharp increase, and at further addition of DoTAC a highly
viscoelastic solution was formed. At a molar fraction corre-
sponding to r ) 0.30 the turbid solution appears (see above).
On the DoTAC-rich side the viscosity decreases at the same
time as the concentration of micelles increases.
As also mentioned in previous sections, the surfactant
aggregation numbers can be estimated from the TRFQ data only
if the free surfactant concentration is known. Three regions
can be identified: the HMHEC system containing only SDS,
the HMHEC system containing only DoTAC, and the HMHEC
system containing a mixture of the two surfactants. In the first
system the free SDS concentration was estimated to 6 mM (see
above); in the second system the free DoTAC concentration
can be estimated to be close to the cmc (20 mM). The latter is
based on the assumption that DoTAC has a cac of ca. 20 mM
in the EHEC system and HEC is expected to interact to a lower
degree.31 In the third case the free surfactant concentration may
be neglected because addition of an oppositely charged surfac-
tant to a solution containing an ionic surfactant usually gives a
Nilsson et al.
dramatic decrease in the cmc. Lucassen-Reynders et al.43
measured surface tension on mixtures of SDS and DoTAB. They
found that the cmc40 decreased from 8.1 mM for SDS and 15
mM for DoTAB to below 0.1 mM already at minor addition of
DoTAB to SDS.
The estimated aggregation numbers at the different conditions
are presented in Table 2. It was found that the aggregation
number increases substantially when SDS is exchanged with
DoTAC. It was also found that at the pure DoTAC solution (r
) 1.0) the concentration of micelles is less than that observed
at the pure SDS solution (r ) 0). However, this can be
explained by the difference in cmc for the two surfactants, 8.1
mM for SDS and 20.0 mM for DoTAC,40 and by the difference
in aggregation number; see Table 2. It is important to note
that at the highest SDS concentration that was used the
concentration of (mixed) micelles is approximately the same
as the concentration of polymer hydrophobic tails. Therefore,
already at such rather low concentrations of SDS, free surfactant
micelles may form.
When the aggregates are too large (r ) 0.25), eq 3 is no
longer suitable to fit the fluorescence decay data as suggested
by the large χ2 value in Table 1. However, a graphical analysis
as described in the Methods section gave quantitatively the same
results as the evaluation with eq 3.
From the high viscosity and the large aggregation number at
surfactant ratios above r ) 0.25, we expect the samples to
contain larger aggregates. This is supported by pictures taken
with cryo-transmission electron microscopy (cryo-TEM44,45).
The data, which will be published in a separate paper, reveals
the presence of vesicles in samples at r ) 0.3. The existence
of large aggregates in the solution is in agreement with findings
by Kamenka et al. and Herrington et al. in surfactant mixtures
of DoTAB and SDS (without polymer).18,41
Comparison between the Three Different Systems: HM-
HEC-SDS, HMHEC-SDS-NaCl, and HMHEC-SDS-
DoTAC. The results from the former sections are replotted
and summarized in Figure 6, where the viscosity in the three
different systems is given as a function of the concentration of
mixed micelles. (These numbers can easily be transferred to
an average number of polymer hydrophobic tails per mixed
micelle (Table 2).) The most important result from Figure 6 is
that the qualitative behavior is the same regardless of the
molecular details of the mixed micelles. This fortifies conclu-
sions drawn in previous investigations,8,10 i.e., that the stoichi-
ometry in the mixed micelles is the most important factor in
determining the rheology of the solution. However, there exist
differences which suggest that other factors have an influence.
In the reference system, the rheology can be expected to have
contributions from an electrostatic swelling due to the charged
surfactants which are bound in the mixed micelles (compare
with the macroscopic swelling of covalently bonded gels upon
addition of ionic surfactants46). The swelling of the polymer
matrices can be expected to increase the viscosity. This is
probably a reason to why the viscosity always is lower in
solutions with screening electrolyte as compared to the solutions
only containing SDS. In line with this and as was mentioned
above, the decrease in viscosity at high concentration of
electrolyte probably reflects the vicinity to the phase separation
due to screening. Another reason to the lower viscosity than
that observed in the reference system may be the larger
surfactant aggregation numbers (see Table 2). Intraaggregation
of polymer tails may be expected to be more frequent with a
big mixed micelle (lowering the probability of interaggregation).
Both the discussed mechanisms (lower electrostatic swelling
Solutions of Surfactant and Modified Polymer
and larger aggregation numbers) may be responsible for the
lower viscosity in the systems containing mixtures of oppositely
charged surfactants as compared to the HMHEC-SDS system.
Conclusions
In this work we have controlled the viscosity by varying the
aggregate size of the mixed micelles with the intention of
providing principles of optimizing rheological properties of
mixtures of hydrophobically modified polymers and surfactants.
In the reference system (HMHEC + SDS) the maximum in
viscosity appears in a small concentration interval. Already
small amounts (20 mm) of surfactant decreases the viscosity
dramatically from the maximum value (located at 7 mm). We
have shown that it is possible to regain a higher viscosity simply
by changing the stoichiometry between polymer hydrophobic
tails and mixed micelles. From the present investigation it
follows that this is an important parameter for the understanding
of the rheological behavior, but it was also shown that other
mechanisms had to be invoked. Most likely electrostatic effects
as well as effects from large aggregation numbers of the mixed
micelles have an influence.
The behavior in viscosity and aggregation number of the
HMHEC-SDS system was shown to be similar to that of the
HMEHEC-SDS system earlier reported.9 In particular, the
increase in viscosity mainly originates from an improved
packing of the amphiphilic molecules in the surface of the mixed
micelles. The decrease in viscosity at higher surfactant
concentrations originates from a rearrangement such that the
intermolecular connectivity decreases when the concentration
of mixed micelles increases.
Acknowledgment. Johan Borgström is gratefully acknowl-
edged for his cryo-TEM expertise. We thank Eduardo Marques
for many useful discussions on vesicles and oppositely charged
surfactants. Thanks also to Ingegerd Lind for her kind technical
assistance. Financial support from the NUTEK and Industry
Sponsored Centre for Amphiphilic Polymers (CAP) is gratefully
acknowledged.
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