Journal of Colloid and Interface Science 367 (2012) 272–279

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Journal of Colloid and Interface Science

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Micellar evolution in mixed nonionic/anionic surfactant systems

Shaohua Lu, Jun Wu, Ponisseril Somasundaran ⇑
NSF Industry/University Cooperative Research Center (I/UCRC) for Particulate and Surfactant Systems at Columbia University, New York, NY 10027, United States

a r t i c l e i n f o a b s t r a c t

Article history: Surfactant mixtures are widely used in industrial applications due to their favorable synergistic interac-
Received 19 April 2011 tions. For instance, anionic and nonionic mixtures are often employed in detergent, personal care, and
Accepted 22 August 2011 enhanced oil recovery. It is useful to understand micellization behaviors of such mixtures, as they are
Available online 7 November 2011
important for formulation optimizations. A range of techniques including surface tensiometry, fluores-
cence spectroscopy, ultrafiltration, and analytical ultracentrifugation (AUC), were employed in this work
Keywords: to obtain information on the micellization behaviors of the mixed n-dodecyl-b-D-maltoside (DM)/sodium
Surfactant mixture
dodecyl sulfonate (SDSN) system. The interaction parameter, monomer concentration, and micellar size
Micellization
Surface tension
and shape distribution were obtained for this mixed surfactant system as a function of total surfactant
Fluorescence concentration as well as mixing ratio to achieve a full understanding of their aggregation behaviors.
Analytical ultracentrifugation The coexistence of two types of micelles was identified in this mixed anionic/nonionic surfactant system
for the first time. A model is proposed to explain such coexistence based on the surface activities and the
interactions between the two types of surfactants. These findings are useful for optimizing the composi-
tion of mixed surfactant systems and enhancing the synergetic efficiency of the system to achieve more
effective and economical formulations.
Ó 2011 Elsevier Inc. All rights reserved.

1. Introduction Nonionic/anionic surfactant mixtures are the dominant combi-

Surfactants are used invariably as mixtures due to economical
and synergistic reasons; however, the synergistic or antagonistic
interactions among the components are not fully understood. Ideal
mixing is usually found to exist only in mixtures of the same type
of surfactants. In the past, researchers have focused on systems
with different types of surfactants. Although the interfacial and
micellization behavior of surfactant mixtures have been investi-
gated for decades, little is known about the structure–performance
relationships of surfactant mixtures. It is well accepted that mixed
micelles can form in surfactant mixtures, and the mixture can be-
have like a new single surfactant with a new CMC, which is deter-
mined by the molar ratio and surface activity of each species;
however, the size and shape of the mixed micelles may be very dif-
ferent from those of the individual surfactants, the determination
of which can be quite a challenge. From the point view of entropy,
the formation of mixed micelles reduces the system energy.
Depending on the intermolecular interactions between the mixed
surfactant species, a single micelle type may not have the lowest
energy. It is important to obtain quantitative information and elu-
cidate the mechanism of assembly of mixed surfactant micelles.
⇑ Corresponding author. Fax: +1 212 854 8362.
E-mail address: ps24@columbia.edu (P. Somasundaran).
nation in commercial surfactant systems, such as detergents [1]
and surfactant fluids for enhanced oil recovery.
In the past, various surfactant mixtures containing sugar-based
surfactants have been studied [2,3]. Many techniques, including
NMR [4,5], ultrafiltration [6,7], fluorescence [8], ESR spectroscopy
[9], small angle neutron scattering [10], analytical ultracentrifuga-
tion [11], have been used to characterize these systems. However,
there is still a lack of quantitative knowledge of the micellization of
the mixtures, specifically the micellar size and distribution, aggre-
gation numbers, and how the micellization is governed by the
molecular interactions.
Sodium dodecyl sulfonate (SDSN) is a very typical anionic sur-
factant, and its properties and behaviors represent most anionic
surfactants. n-Dodecyl-b-D-maltoside (DM), a sugar-based surfac-
tant, is biodegradable, environmentally benign, and has drawn a
great deal of attention in surfactant research. In this work, the mix-
tures of these two surfactants were investigated using a range of
techniques including surface tensiometry, fluorescence spectros-
copy, ultrafiltration, and analytical ultracentrifugation. Surface
tensiometry provides traditional information on the surface activ-
ity of the mixtures and thus, molecular packing and interaction
parameters. Fluorescence technique provides quantitative infor-
mation of the onset concentration of micellization. Ultrafiltration
technique quantifies the monomer concentration of each surfac-
tant in their mixtures at various concentrations and mixing ratios.
Analytical ultracentrifugation provides quantitative information
on micellar size, distributions, and aggregation numbers. The

0021-9797/$ - see front matter Ó 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2011.08.050
 S. Lu et al. / Journal of Colloid and Interface Science 367 (2012) 272–279 273

coexistence of two types of micelles was successfully identified
using this technique. The information obtained in turn helps us
understand the application of the mixture.
2. Experimental
2.1. Materials
Surfactants: n-Dodecyl-b-D-maltoside (DM) of 98% purity grade
was obtained from Calbio chem and sodium dodecyl sulfonate
(SDSN) of greater than 99% purity and purchased from TCI Chemi-
cals, Japan, were used as received. Fresh SDSN stock solutions were
prepared in each experiment.
Water, used in all of the experiments, was triple distilled with a
specific conductivity of less than 2.5 lX1 and was tested for the
absence of organics using surface tension measurements.
2.2. Surface tension
The surface tension of nonionic and anionic surfactants and
their mixtures was measured at 25 ± 1 °C with the Wilhelmy plate
technique using a sandblasted platinum plate as the sensor. For
each measurement, the sensor was in contact with the surfactant
solution for 30 min to allow equilibration.
2.3. Fluorescence experiments
2.3.1. Sample preparation
For fluorescence measurements, the surfactant solutions were
mixed with the desired amount of pyrene to make the final pyrene
concentration 1.0 lM. Surfactant solutions containing pyrene
were shaken overnight at room temperature before taking fluores-
cence spectroscopy.
2.3.2. Steady-state experiments
Steady-state emission spectra were obtained using a Horiba Jo-
bin Yvon Fluorolog FL-1039 spectrophotometer. A portion of the
surfactant solution sample containing pyrene was transferred to
quartz cells, the samples were excited at 335 nm, and their emis-
sions between 360 and 500 nm were recorded.
2.4. Density measurement
The partial specific volume of surfactant micelles, necessary for
the analysis of analytical ultracentrifuge data, was obtained by cor-
relating the density to the solution concentration. The density of
the solutions was measured using an Anton Paar density meter.
The accuracies of the density and temperature data are
±5  106g/cm3 and ±0.01 °C, respectively. The density of fresh, tri-
ple-distilled water was measured to be 0.99703 ± 0.000005 g/cm3
at 25.00 °C. Acetone was used to rinse the sample chamber be-
2.6. Analytical ultracentrifugation (AUC) experiments
Sedimentation velocity tests were performed using a Beckman
Coulter Optima XL-I analytical ultracentrifuge, equipped with both
absorbance and interference optical detectors. A 12 mm two-chan-
nel aluminum cell and quartz windows were used for velocity
experiments. Three aluminum cells and a reference cell were coun-
terbalanced in an An-60 Ti rotor. The rotor speed was set at
40,000 rpm and the temperature was maintained at 25.0 °C. The
tests were run after the vacuum reached below 5 lmHg
(0.65 Pa). SEDFIT 92 software developed by Schuck [15] was used
for the sedimentation velocity data analysis.
3. Results and discussion
In this paper, the anionic and nonionic surfactant mixture was
studied using various techniques including surface tensiometry,
ultrafiltration and analytical centrifugation, which can provide un-
ique information on micellar size and distribution. Although it is
commonly agreed that multi surfactants can form mixed micelles,
there is little information known on their properties such as micel-
lar shape, size, and aggregation number of each species in the
micelles.
3.1. Surface tension measurements
The equilibrium surface tensions of mixed DM/SDS systems
were determined using a plate method. Results obtained for the
surface tension of aqueous solutions of DM, SDSN, and their mix-
tures are given in Fig. 1. The DM molar ratio, a, was varied from
1.00, 0.75, 0.50, 0.25, 0.10 to 0. The onset of the plateau range on
the surface tension-concentration curves was considered to indi-
cate the CMC in each case.
Clearly, the surface activity of the mixture system decreases
with a decrease in DM molar ratio, however, even at molar ratio
0.10, the CMC value is 10 times lower than that of SDSN alone.
The area occupied by surfactant molecules at water/air interface
can be estimated using Gibbs equation. The area of adsorbed DM
alone was found to be 46 Å2 per molecule, while it is 58 Å2 per mol-
ecule for SDSN.
Based on the surface tension results, the interaction parameter
b is calculated using regular solution theory [16–19].
x21 lnða1 C 12 =x1 C 1 Þ
2
¼1 ð1Þ
ð1  x1 Þ ln½ð1  a1 ÞC 12 =ð1  x1 ÞC 2 
75
DM ratio α
1.00
70
0.75
65 α=0.10 0.50
Surface Tension (mN/m)

0.25
tween measurements and the chamber was dried by pumping fil- 60 α=0.50 0.10
tered air into it. α=0.25 α=0 0
55 α=0.75

2.5. Ultrafiltration 50 α=1.00

45
Ultrafiltration technique has been used successfully to separate
surfactant monomers from micelles during the last two decades to 40
understand the micellization behavior of surfactant mixtures o
[6,7,12–14]. All ultrafiltration tests were done at room tempera- 35 25 C
no salt
ture (23 ± 2 °C) using Amicon YM-3 membranes specified to ex-
30
clude molecules with molecular weights greater than 3000 with 10-5 10-4 10-3 10-2
a diameter 44.5 mm. The filtration was carried out using an Ami- Total surfactant concentration (M)
con model 8050 filter at a 380-mmHg nitrogen pressure. A 2.0 ml
of permeate was filtered from 20.0 ml sample solution. Fig. 1. Equilibrium surface tension curves of mixed DM/SDSN systems.
274 S. Lu et al. / Journal of Colloid and Interface Science 367 (2012) 272–279

lnða1 C 12 =x1 C 1 Þ 1.0

b¼ ð2Þ DM ratio α
ð1  x1 Þ2
1.00
0.9 0.75
where x1 is the mole fraction of surfactant 1 in mixed micelles, a1 is 0.50
the mole fraction of surfactant 1 in solutions at total concentrations, 0.25
0.8 0.10
C1, C2, and C12 are CMCs for surfactants 1, 2, and their mixtures.
0

I3/I1 ratio
Table 1 lists the CMC, DM molar ratio in mixed micelles x1
α=0.25
and interaction parameter (b) for DM/SDSN mixtures with differ- 0.7 α=0.10 α=0
ent mixing ratios. The calculated b parameter lies between 2.2
and 3.2, suggesting that the interaction between DM and SDSN α=0.50
is weaker than the interaction between DM and sodium dodecyl 0.6
α=1.00
sulfate with a b parameter between 3.3 and 4.0 [8]. It was
α=0.75 o
observed that the higher the DM molar ratio in total surfactant 25 C
0.5
concentration, the greater the DM molar ratio is in micelles, no salt
and the stronger the interaction between DM and SDSN. The sur-
10-5 10-4 10-3 10-2
face activity is obviously controlled by the molar ratio in the
Total surfactant concentration (M)
case of mixtures, and the lower the ratio of the more active
component, the lower the surface activity of the mixtures. This Fig. 2. Variation of polarity parameters as indicated by I3/I1 ratio at different mixing
result is important for many industrial processes such as en- ratios.
hanced oil recovery. By varying the mixing ratio (formula), the
optimal balance between surface activity and chemical loss in
EOR can be achieved. 3.3. Monomer concentration changes in mixed DM/SDSN system

In surfactant solutions, the micelles are in equilibrium with

monomer surfactant molecules. Information on the monomer con-
3.2. Fluorescence measurements
centrations helps to understand the aggregation behavior of mixed
DM/SDSN systems. Even though monomer concentrations of single
Fluorescence spectroscopic technique is used to obtain polarity
surfactant systems have been studied extensively, the investiga-
information on the nanostructure of the aggregates of mixed sur-
tion of mixtures is scarce.
factants. The polarity parameter of probe molecules reveals infor-
In this study, the monomer molecules were first separated from
mation of hydrocarbon tails packing in the micellar cores. In
bulk using the ultrafiltration technique. The membranes employed
fluorescence spectroscopy, dependency on the polarity of the envi-
were specified to exclude molecules with molecular weights great-
ronment around the probe [20] is shown by the ratio of relative
er than 3000. A small amount of solution was collected for each
intensities of the I1 (373 nm) and I3 (383 nm) peaks (I3/I1) in a pyr-
sample to avoid significant increase in equilibrium surfactant con-
ene emission spectrum. This ratio decreases as the polarity in-
centration. The permeates were then analyzed to determine the
creases and can be used to estimate the polarity of the
concentration for each component, respectively. The experiments
environment; thus, the ratio can detect the presence of surfactant
were conducted at DM ratios of 0.75, 0.50, and 0.25. The results
aggregates in the solution. The polarity parameter of pyrene is
are shown in Fig. 3.
shown in Fig. 2 as a function of surfactant concentration. At low
Based on the regular solution theory developed by Holland and
concentrations for each system, the value of I3/I1 ratio corresponds
Roubingh, the monomer concentrations of a binary surfactant mix-
to that of water (0.5–0.6). At certain concentrations, there is a rapid
ture can be estimated using the following equations:
increase in the value of the I3/I1 ratio indicating the formation of
The molar fraction of surfactant 1 in the mixed micelle can be
micelles. The CMC of the surfactant mixtures obtained from fluo-
calculated using the equation,
rescence tests is in agreement with those obtained from surface qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
tension measurements. ðC  D þ ðC  DÞ2 þ 4aC D
The polarity parameter of the pyrene at concentrations above x1 ¼ ð3Þ
2D
CMC provides information on the hydrophobic structure of the mi-
celles. In the DM/SDSN system, the I3/I1 ratio for SDSN is higher where D ¼ f2 C 2  f1 C 1 , f1 and f2 are the activity coefficients of sur-
than that for DM above CMC, suggesting that the core of SDSN mi- factant 1 and 2 in the mixed micelle respectively and can be calcu-
celles is more hydrophobic than that of DM micelles but less lated as:
hydrophobic than that of pure hydrocarbons (>1.1). The I3/I1 polar-
f1 ¼ expðbð1  x1 Þ2 Þ ð4Þ
ity parameter of the micelles decreases with an increase in the DM
ratio in the mixtures below a certain concentration. In the plateau
f2 ¼ expðbx21 Þ ð5Þ
range, the polarity parameter increases with concentration, sug-
gesting a transition from DM-rich micelles to SDSN-rich micelles. The monomer concentrations can be then calculated as:
Compositional change of the mixed micelles is determined by the
intermolecular interactions between the surfactants. CM
1 ¼ xf1 C 1 ð6Þ

Table 1
Parameters of DM/SDSN system obtained from surface tension data analysis.

DM/SDSN 1:0 3:1 1:1 1:3 1:9 0:1

CMC (M) 0.00018 0.00022 0.00031 0.00054 0.00109 0.01150
CMC (theory) 0.00024 0.00035 0.00069 0.00158
x1 0.9352 0.8872 0.8162 0.7203
b 2.9676 2.7051 2.4712 2.2890
 S. Lu et al. / Journal of Colloid and Interface Science 367 (2012) 272–279 275

1.0 -4
2.0x10
-4
Experimental DM concentration:5.0×10 M
α=0.75 DM ratio α
0.8 β=−3.0 0.75

DM monomer concentration (M)

0.50 1.5x10
-4
DM Ratio in monomers (M)

β=0
0.25
0.6 α=0.50
β=−2.7
1.0x10
-4 β=-1.0

0.4 β=-2.0
α=0..25
β=-3.0
β=−2.5 -5
5.0x10
0.2
β=-6.0 β=-5.0
β=-4.0
Experimental
0.0 0.0
-5 -4 -3 -2 -1
10 10 10 10 10 0.0 1.0x10-3 2.0x10-3 3.0x10-3 4.0x10-3 5.0x10-3
Total surfactant concentration (M) Total surfactant concentration (M)

Fig. 3. DM ratio in monomers as a function of total surfactant concentration. Fig. 4. DM monomer concentration as a function of total surfactant concentration
Symbols represent the experimental data using ultrafiltration, and the dashed lines (DM concentration was fixed at 5.0  104 M). The symbols represent the exper-
are predicted using regular solution theory using the interaction parameters imental data, and the dashed lines represent the results predicted using regular
obtained from surface tension measurements. solution theory using various interaction parameters.

CM
1 ¼ ð1  xÞf2 C 2 ð7Þ wards, the results were analyzed using sedfit92 software. As a non-
ionic surfactant, DM forms larger micelles than SDSN; this is
The calculated results were found to be in agreement with the
attributed to the electrostatic repulsion among SDSN head groups
experimental data in the ranges above CMS as shown in Fig. 3.
that limits the micellar growth.
The DM monomer ratio is seen to decrease with the increase in to-
tal surfactant concentration when mixed micellization occurs. Reg-
3.5. Partial specific volume
ular solution theory only predicts the monomer concentration
above CMC and assumes no micelles below it. The experimental re-
Since the sedimentation velocity of the surfactant micelles is
sults show a maximum of DM monomer ratio in the concentration
determined mainly by the density of the surfactant micelles, data
range below but close to CMC. As the cut-off molecular weight of
for partial specific volume is required for analysis of the analytical
the membrane used is 3000, premicelles may pass through the
ultracentrifugation data to calculate sedimentation coefficient and
pores and be accounted as monomers. This occurrence might be
the micelle mass. The partial specific volume v  is obtained empir-
evidence for the existence of dimers or premicelles as reported in
ically from the density gradient using the following equation:
literature [21], but further investigation is needed.
 
To further understand the correlation between monomer con- 1 dq
centration and mixing ratio, monomer concentration was studied
v ¼ 1 ð8Þ
q0 dC
at various surfactant ratios. The DM concentration was fixed at
5.0  104 M, while the SDSN concentration was varied from 0 to where C is the surfactant volumetric concentration in grams per
3.0  103 M. The DM monomer concentration was found to de- milliliter; q and q0 are the densities of the solution and the solvent,
crease sharply with the increase in the SDSN ratio shown in respectively.
Fig. 4. Also, the DM monomer concentration was calculated using The density of DM and SDSN solutions was measured using an
regular solution theory using different interaction parameters, b, Anton Paar 5000A densitometer, and the results are shown in
from 0 to 6.0. Interestingly, it was found that the experimental Figs. 5 and 6.
data crossed over the curves from 6.0 to 4.0, suggesting a de-
crease in the interaction parameter with an increase in the SDSN
ratio, which is consistent with the results obtained from surface Y=0.99705+0.18371*X
1.00230
tension measurements. R=0.99996
Solution density (g/ml)

1.00100
3.4. Micellar size and shape using analytical ultracentrifuge (AUC)

It is useful to get information on the size and shape of the sur- 0.99970
factant aggregates to elucidate the interaction and molecular pack-
ing in surfactant mixture systems. In literature, several techniques
0.99840
including light scattering [22], small angle neutron scattering
(SANS) [23], and Cryo-TEM [24] techniques have been employed
to obtain such information. However, they are somewhat inade- 0.99710 25.0 C
o

quate on a nanometer-scale (especially below 10 nm).

Here, analytical ultracentrifugation technique was employed to 0.0 5.0x10
-3
1.0x10
-2
1.5x10
-2
2.0x10
-2
2.5x10
-2
3.0x10
-2

monitor micelle formation in terms of aggregate number, size, and DM concentration (g/ml)
shape. The experiments were conducted at 40000 rpm and 25.0 °C.
The sedimentation velocity curves were scanned for 15 h. After- Fig. 5. Density-concentration results for DM solutions.
276 S. Lu et al. / Journal of Colloid and Interface Science 367 (2012) 272–279

By fitting the density-concentration data using Eq. (8), the spe- 8

cific volumes for DM and SDSN were calculated to be 0.833 ml/g Conc.: 10.0mM DM/SDSN
1:3 o
and 0.826 ml/g, respectively. Clearly, the values for these two sur- 25.0 C 1:0
factants are very close; therefore, the mixed DM/SDSN micelles can 1:9 9:1
be expected to have a specific volume value around 0.830 ml/g, 6 3:1
which was used in the data analysis of the sedimentation velocity 1:1
1:3

Distribution C (s)
method.
1:1 1:0 1:9
4
3.6. Size distributions of mixed DM/SDSN systems
3:1

Based on the sedimentation process of the micelles, information

on the size and shape of the species can be obtained. The size dis- 2
9:1
tributions of mixed DM/SDSN micelles at 10.0 mM are shown in
Fig. 7 as a function of the sedimentation coefficient. In the case
of DM alone, a single peak was observed around 3.6 S. Since SDSN 3:1 9:1
alone does not form micelles at this concentration, no sedimenta- 0
tion process was observed. The micellar distribution shifts to a 1 2 3 4 5

lower sedimentation coefficient range with increases in the SDSN Sedimentation Coefficient, s (Svedberg)
molar ratio, suggesting a decrease in micellar size. The micellar
Fig. 7. Size distributions over sedimentation coefficient for mixed DM/SDSN
evolution can be attributed to the nature of the surfactant mole- systems at 10.0 mM.
cules. Since the SDSN molecules are charged, the electrostatic
repulsion hinders the association of molecules, while the micelliza-
tion of DM is determined only by the effective geometry of the 10
molecule. Conc.: 50.0mM DM/SDSN
1:3 o
Interestingly, a second micellar peak was observed at the DM/ 25.0 C 1:0
SDSN ratios of 9:1 and 3:1 suggesting the existence of a second 3:1
8
micellar species. Even though the coexistence of two types of mi- 1:1 1:1
1:0 1:3
celles has been predicted in the past [25], this is the first report
of direct evidence of the coexistence of micellar species in mixed
Distribution C (s)

6
nonionic/anionic surfactant mixtures. This phenomenon can be
3:1
understood using the schematic model proposed by Huang and
Somasundaran [6,26]. At a high DM ratio, the concentration of 9:1
4
SDSN (at 9:1 ratio, 1.0 mM; at 3:1 ratio, 2.5 mM) is far below its
CMC (11.5 mM); therefore SDSN itself does not form micelles,
and the formation of mixed aggregates is proposed to be due to
the dissolution of SDSN molecules into the DM micelles. As re- 2 Second Species
vealed by the results of ultrafiltration measurements given in
Fig. 3, the monomer ratio of SDSN is larger than the overall SDSN 3:1 1:1 9:1
ratio in the whole mixture, suggesting a low ratio of SDSN in the 0
0 1 2 3 4 5 6
micellar phase. Since the second peaks are very close to the peak
Sedimentation Coefficient, s (Svedberg)
of DM, it is proposed that some DM-rich micelles exist in equilib-
rium with the mixed micelles (the first peak). In addition, it can be Fig. 8. Size distributions over sedimentation coefficients for mixed DM/SDSN
seen that the area of the second peak is very small, indicating a low systems at 50.0 mM.
molar ratio of the second micellar species under the conditions.
The size distributions of mixed DM/SDSN at 50.0 mM are shown
in Fig. 8. The results are similar to those at 10.0 mM; however the peaks appear at a lower sedimentation coefficient range. Since
50.0 mM is above the solubility of SDSN at room temperature, the
peak for the pure SDSN micelle was not obtained. The peaks were
0.99720 also found to shift from right to left with an increase in SDSN molar
Y=0.99705+0.17336*X ratios. The coexistence of two types of micelles was also observed at
R=0.99909 50.0 mM at DM/SDSN ratios of 9:1, 3:1 and 1:1. This behavior is also
0.99715 proposed to be due to the existence of the DM-rich micelles.
Solution density (g/ml)

Beside the size distribution, the shape of the mixed micelles

was identified as spherical in the concentration range and mixing
ratios tested. The shape is determined by the packing parameter.
0.99710
Since both DM and SDSN have relatively large headgroups, the
mixed micelles have a high packing curvature. In the cases of mix-
tures, the mixed micelles still have a high curvature and possibly
0.99705 have a spherical shape even though synergistic interactions exist
between DM and SDSN.
o
25.0 C
0.99700
0.0 1.0x10
-4
2.0x10
-4
3.0x10
-4
4.0x10
-4
5.0x10
-4
6.0x10
-4
7.0x10
-4 3.7. Aggregation numbers of mixed DM/SDSN systems
SDSN concentration (g/ml)
Aggregation number is an important parameter for surfactant
Fig. 6. Density-concentration results for SDSN solution. micelles. In the past, a number of techniques have been employed
 S. Lu et al. / Journal of Colloid and Interface Science 367 (2012) 272–279 277

to determine the aggregation number of the surfactant mixture Mixed DM/SDSN Total Concentration: 50.0mM
system, including small angle neutron scattering (SANS), light scat- 1.00
o
tering, and static and life-time fluorescence spectroscopies. How- 25.0 C 4%
240
ever, the accuracy does not appear to be satisfactory, especially 5%
for spherical micellar systems. Based on the size distributions Aggregation number 0.80

shown in Figs. 7 and 8, the micellar mass was obtained, and then 200 of second species

Aggregation number

DM ratio in micelles
the aggregation number was calculated by dividing micellar mass
by the molecular weight. In the cases of mixtures, the monomer 160 0.60
1%
concentrations were used to estimate the molar ratio in the micel-
lar phase so that the average molecular weight can be calculated. 120
The aggregation numbers of the mixed DM/SDSN systems at 0.40

10.0 mM are shown in Fig. 9 as a function of DM ratio. The DM ratio 80 Aggregation number
in the micellar phase was found to increase correspondingly with
of first species 0.20
its bulk counterpart. The aggregation number of the mixed system
40
is significantly lower than that of DM even with a low percentage
of SDSN. DM alone has an aggregation number above 100, but the
aggregation number (primary micelle type) in the mixture is be- 0 0.00
0.00 0.20 0.40 0.60 0.80 1.00
tween 40 and 60, which is close to the aggregation number of pure
DM ratio
SDSN micelles reported in the literature [27]. This phenomenon
suggests that the presence of electrostatic repulsion weakens the Fig. 10. Aggregation numbers and DM ratio in micellar phase for mixed DM/SDSN
association of surfactant molecules by altering the packing curva- system at 50.0 mM.
ture. At a high DM ratio, the SDSN ratio in the micellar phase is
very low, as most of the SDSN molecules exist as monomers. As
significant role in determining the micellar size and shape. To fur-
shown in Figs. 7 and 8, the mixed micelles show a size distribution,
ther understand the effect of the surfactant concentration on the
which indicates that the SDSN molecules are not uniformly distrib-
micellization of a mixed DM/SDSN system, surfactant mixtures at
uted in the mixed micellar phase, and there may exist an equilib-
1.0 mM and 30.0 mM were investigated using analytical ultracen-
rium between DM-only micelles and mixed micelles when the
trifugation. The results are shown in Fig. 11 along with the results
SDSN ratio is low in the micellar phase. The DM-only micelles
obtained at 10.0 mM and 50.0 mM.
are identified experimentally as the secondary species with a large
It is clear that at a 1:1 ratio the mixed DM/SDSN micelles be-
aggregation number as shown in Fig. 9.
come smaller with an increase in total surfactant concentration.
The aggregation numbers at 50.0 mM are shown in Fig. 10 along
Furthermore, only one type of micelle was observed at 1.0 mM
with the DM ratios. A sharp increase in the aggregation number
and 10.0 mM, while two types were seen to coexist at 30.0 mM
was found above a DM ratio of 0.75, below which the presence
and 50.0 mM. The nature of micellar evolution observed at differ-
of SDSN molecules produces enough electrostatic repulsion to limit
ent concentrations is attributed to the interaction between DM
the incorporation of additional molecules to the micelles. Even
and SDSN molecules. SDSN does not form micelles at concentra-
though the second micellar species is only a small portion of micel-
tions lower than its CMC, while it can be dissolved into the DM mi-
lar species (lower than 5%), their aggregation numbers were found
celles forming mixed aggregates. Also, the ratio of SDSN in the
to be much larger than even those of DM alone.
monomer is high at low concentrations indicative of a low ratio
of it in the micellar phase. With an increase in concentration, more
3.8. Micellar evolution in mixed DM/SDSN systems
SDSN molecules are incorporated into the micellar phase causing
an enhancement in the electrostatic repulsion, which in turn re-
From the results of aggregation numbers at 10.0 mM and
sults in the shrinking of the mixed micelles. On the other hand,
50.0 mM, it can be seen that the surfactant concentration plays a

Mixed DM/SDSN Total Concentration: 10.0mM 10

240 1.00 DM/SDSN = 1 : 1 Conc.
o
25.0 C 13% o
50mM 25.0 C 1.0mM
Aggregation number 8 10.0mM
200 of second species 0.80 30.0mM
50.0mM
Aggregation number

DM ratio in micelles

Distribution C (s)

160 6
14% 0.60
30 mM

120
0.40 4 1mM
Aggregation number
of first species 10mM
80
0.20 2

40
50mM
0.00 0
0.00 0.20 0.40 0.60 0.80 1.00 0 1 2 3 4 5
DM ratio Sedimentation Coefficient, s (Svedberg)

Fig. 9. Aggregation numbers and DM ratio in the micellar phase of a mixed DM/ Fig. 11. Effects of surfactant concentration on the size distributions of mixed DM/
SDSN system at 10.0 mM. SDSN systems.
278 S. Lu et al. / Journal of Colloid and Interface Science 367 (2012) 272–279
Nagg of first species
250 3%
Nagg of second species
200
Aggregation number
4%
150
100
DM/SDSN = 1 : 1
o
25.0 C
50
0 0.00
0.00 0.01 0.02 0.03 0.04
Surfactant Concentration (M)
Fig. 12. Effects of concentration on aggregation numbers and DM ratio in the
micellar phase for the mixed DM/SDSN system.
the possibility of forming DM-rich micelles increases with total
surfactant concentration, which is shown as the second micellar
species with a large aggregation number.
The aggregation numbers of mixed DM/SDSN at a 1:1 mixing ra-
tio are plotted in Fig. 12 along with the DM ratio in the micellar
phase. Interestingly, the aggregation number decreases with an in-
crease in surfactant concentration as well as the DM ratio in the
micellar phase. It is clear that the aggregation number of mixed
DM/SDSN micelles correlates with the DM ratio in the micellar
phase. At low concentrations, the DM molecule is the dominating
component in the mixed micelles, and the electrostatic repulsion
between SDSN molecules is screened by the presence of uncharged
DM molecules. With an increase in the concentration, more SDSN
molecules are incorporated into the mixed micelle. The electro-
static repulsion begins to take place, causing the disassembly of
surfactant micelles. With further increase in the surfactant concen-
tration, DM-rich micelles appear as the second species (see Fig. 13).
4. Conclusions
The interfacial and solution properties of mixed nonionic n-
dodecyl-b-D-maltoside and anionic sodium dodecyl sulfonate sys-
tems were investigated using a number of techniques including
surface tensiometry, fluorescence spectroscopy, ultrafiltration,
and analytical ultracentrifugation. The experimental data were
Solubilization of SDSN molecules in DM micelles at low concentration
+ +
Coexistence of DM-rich micelles at high concentration
Fig. 13. Illustration of micellization of mixed DM/SDSN systems.
1.00 compared with the results predicted using the regular solution
theory. The following conclusions were reached:
0.80 1. The surface activity and the non-ideality of this mixture were
studied using surface tensiometry. A considerable synergistic
DM ratio in micelles
interaction was identified and quantified as an interaction
0.60 parameter, b, which varies from 2.0 to 3.0 depending on
the mixing ratio. The fluorescence results reveal the onset con-
centration of micellization and are consistent with surface ten-
0.40 siometry results. Analysis of the surface tension curves using
the Gibbs equation suggests a spherical shape for both DM
and SDSN micelles.
0.20 2. Ultrafiltration technique was successfully employed to separate
surfactant monomers from the bulk. The theoretical results pre-
dicted using regular solution theory were found to agree with
the experimental data above their CMC’s, even though the
0.05
interaction parameter was found to vary significantly with the
mixing ratio. The maximum DM monomer ratio may indicate
the onset of dimers or premicelles in the concentration ranges
below CMC, but further investigation is needed.
3. Analytical ultracentrifugation technique was used for the first
time to investigate this nonionic/anionic surfactant mixture.
The micellar shape and size distribution of mixed DM/SDSN
were obtained at various mixing ratios and concentrations.
The micellar size was found to decrease with an increase in
SDSN ratio due to the electrostatic repulsion between the
charged SDSN molecules. The micellar shape was found to be
spherical in the range that was tested, and this finding was con-
sistent with the prediction based on the area of adsorption at
the water/air interface. Interestingly, the coexistence of two
types of micelles was observed at high surfactant concentra-
tions in DM/SDSN systems. Even though the second species
has a low population (<4%), it has a large aggregation number
up to 220. The aggregation in mixed DM/SDSN systems was
found to be correlated with the DM ratio in the micellar phase.
The findings reported in this paper are of importance in under-
standing the behavior of mixed surfactants. In aqueous solutions,
the non-polar tail of surfactant molecules assemble to form aggre-
gates of reduced total energy. The structure of the micelles is deter-
mined by the geometry of the surfactant molecules and the
intermolecular interactions. The correlation is often represented
by the packing parameter theory; however, the theory is limited
to predict the structure of mixed surfactant micelles, especially
in cases where multiple micellar species coexist as reported in this
paper. Apparently, the mixed micellar species are determined by
multiple factors. As different surfactants have different packing
parameters, and hence different curvatures, there may exist multi-
+
 S. Lu et al. / Journal of Colloid and Interface Science 367 (2012) 272–279
ple curvatures in one single micelles, as we demonstrate in the pa-
per. The high curvature molecules remain in the center, while the
low curvature molecules stay in the two ends of the elliptical mi-
celles (see Fig. 13). This mechanism may also be used to explain
the evolution of surfactant micelles shapes from spherical, ellipti-
cal, cylindrical to even worm-like micelles. The packing parameters
theory can be modified to predict the mixed micellar species.
Acknowledgments
The authors acknowledge the financial support of the National
Science Foundation (Grant Number: IIP-0749461) and the I/UCRC
Center for Particulate and Surfactant Systems at Columbia
University.
References
[1] K.-Y. Lai, Liquid Detergents, second ed., Taylor & Francis, Boca Raton, 2006.
[2] F. Li, M.J. Rosen, S.B. Sulthana, Langmuir 17 (2001) 1037.
[3] M.J. Rosen, S.B. Sulthana, J. Colloid Interface Sci. 239 (2001) 528.
[4] P.C. Griffiths, P. Stilbs, K. Paulsen, A.M. Howe, A.R. Pitt, J. Phys. Chem. B 101
(1997) 915.
[5] Q.Q. Yang, Q. Zhou, P. Somasundaran, Colloids Surf. a – Physicochem. Eng.
Aspects 305 (2007) 22.
279
[6] L. Huang, P. Somasundaran, Langmuir 12 (1996) 5790.
[7] I.W. Osbornelee, R.S. Schechter, W.H. Wade, J. Colloid Interface Sci. 94 (1983)
179.
[8] R. Zhang, L. Zhang, P. Somasundaran, J. Colloid Interface Sci. 278 (2004) 453.
[9] L. Huang, A. Fan, P. Somasundaran, in: Modern Characterization Methods of
Surfactant Systems, New York, 1999, p. 213.
[10] J. Oberdisse, Phys. Chem. Chem. Phys. 6 (2004) 1557.
[11] R. Zhang, P. Somasundaran, Langmuir 20 (2004) 8552.
[12] T. Asakawa, K. Johten, S. Miyagishi, M. Nishida, Langmuir 4 (1988) 136.
[13] G.G. Warr, F. Grieser, T.W. Healy, J. Phys. Chem. 87 (1983) 1220.
[14] A. Makayssi, D. Lemordant, C. Treiner, Langmuir 9 (1993) 2808.
[15] J. Dam, P. Schuck, Numer. Comput. Methods E 384 (2004) 185.
[16] J.H. Clint, J. Chem. Soc. – Faraday Trans. I 71 (1975) 1327.
[17] J.H. Clint, T. Walker, J. Chem. Soc. – Faraday Trans. I 71 (1975) 946.
[18] Y.P. Xi, E.G. Nette, D.W. King, M. Rosen, Mech. Ageing Dev. 19 (1982) 315.
[19] H. Hoffmann, G. Possnecker, Langmuir 10 (1994) 381.
[20] K. Kalyanasundaram, J.K. Thomas, J. Am. Chem. Soc. 99 (1977) 2039.
[21] P. Mukerjee, Adv. Colloid Interface Sci. 1 (1967) 242.
[22] P.R. Majhi, P.L. Dubin, X. Feng, X. Guo, F.A.M. Leermakers, C. Tribet, J. Phys.
Chem. B 108 (2004) 5980.
[23] P. Baverback, C.L.P. Oliveira, V.M. Garamus, I. Varga, P.M. Claesson, J. Pedersen,
Langmuir 25 (2009) 7296.
[24] Y. Talmon, in: B.P. Binks (Ed.), Modern Characterization Methods of Surfactant
Systems, Marcel Dekker, Inc., New York, 1999, p. 147.
[25] R. Nagarajan, ACS Symp. Ser. 501 (1992) 54.
[26] T.N.a.O.K.A. Masahiko, J. Colloid Interface Sci. 107 (1985) 503.
[27] B.C. Bennion, E.M. Eyring, J. Colloid Interface Sci. 32 (1970) 286.