Transactions of Tianjin University

https://doi.org/10.1007/s12209-020-00244-w

RESEARCH ARTICLE

Synergistic Effect of Cocamidopropyl Betaine and Sodium Lauroyl

Sarcosinate
Hongyuan Wei1 · Rui Zhang1 · Zhong Lei2 · Leping Dang1

Received: 2 February 2020 / Revised: 12 February 2020 / Accepted: 24 February 2020

© Tianjin University and Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
In this study, we investigated the synergistic effect of a zwitterionic surfactant (cocamidopropyl betaine) and amino acid
surfactant (sodium lauroyl sarcosinate) by measurements of surface tension, rheological properties, dynamic light scatter-
ing (DLS), and transmission electron microscopy (TEM). The results confirm the formation of wormlike micelles in the
mixed system, which leads to superior surface activity as compared to that of an individual surfactant. Stable and dynamic
viscoelastic measurements were also performed to explore the characteristics of wormlike micelles at different mole frac-
tions, pH values, and temperatures. The results indicate that the strongest wormlike structure formed under the conditions
of X1 = 0.5, pH = 4.7, and CT = 600 mmol/L. The size and morphology of the mixed micelles were obtained by DLS and
TEM. The results of this work offer insight into the interaction between zwitterionic and amino acid surfactants, which will
contribute to the design of complex surfactants.

Keywords Surfactant · Synergistic effect · Rheology · Wormlike micelles

Introduction
Zwitterionic surfactants have drawn much attention due to
their excellent cleaning, conditioning, and antistatic prop-
erties. These properties depend on the pH of the solution
due to the presence of both cationic and anionic hydrophilic
groups in the molecules [1, 2]. Below and above the isoelec-
tric point, zwitterionic surfactants are in the form of cations
and anions, respectively [3]. Recently, the strong synergistic
effect of a mixture of zwitterionic and other anionic sur-
factants has attracted a great deal of interest [4, 5]. These
Electronic supplementary material The online version of this
article (https​://doi.org/10.1007/s1220​9-020-00244​-w) contains
supplementary material, which is available to authorized users.
* Hongyuan Wei
crystallization.wei@hotmail.com
* Leping Dang
dangleping@tju.edu.cn
1
School of Chemical Engineering and Technology, Tianjin
University, Tianjin 300072, China
2
Procter & Gamble Technology (Beijing) Co., Ltd.,
Beijing 101312, China
mixed systems have desirable surface activity and are widely
used in cosmetics, pharmaceuticals, and detergents [6, 7].
The interaction between zwitterionic and anionic sur-
factants has been extensively studied for many years. Praja-
pati and Bhagwat [8] found cocamidopropyl betaine (CAPB)
and sodium lauryl sulfate to exhibit a strong synergistic
interaction in adsorption and micellization. Danov et al. [9]
reported that the combination of zwitterionic and ionic sur-
factants could increase surface elasticity, which could be
used for estimating the thickness and stability of foam films.
The synergistic effect also enhances the salt resistance of
the system and improves the interfacial activity, which has
great significance for the application of surfactants in highly
saline conditions [10].
The addition of oppositely charged amphiphiles reduces
the charge density of surface-mixed micelles, which results
in a reduction in the electrostatic repulsion between sur-
factants [11]. This leads to the formation of a range of
self-assembled aggregates such as spherical or rod-shaped
micelles, vesicles, and different liquid crystalline phases [12,
13]. Among them, the wormlike micelle is a long flexible
aggregate held together by physical bonds that can continu-
ously break and be restored [14]. Due to their unique rheo-
logical properties, wormlike micelle systems have important
applications in cleaning products [15], drag-reducing agents

13
Vol.:(0123456789)

[16], and oilfield fracturing [17]. Chu et al. [18] presented a
review of intelligent wormlike micelles with electrical, opti-
cal, temperature, pH or ­CO2-triggers [19]. Stukan et al. [20]
found wormlike micelles to offer great potential in rheologi-
cal control. Their research results proved that the synergism
of zwitterionic/anionic surfactants can induce the formation
of wormlike micelles, which significantly improves the vis-
coelasticity of the system.
The zwitterionic surfactant CAPB has been widely used as
a foaming booster [21] and thickener in personal care prod-
ucts [22]. Recently, researchers have also found that it can
be applied to achieving biological separation [23] and pro-
tein stability [24]. The amino acid surfactant sodium lauroyl
sarcosinate (SLS) with cleavable amide groups has attracted
great attention for its excellent chemical stability, biodegrada-
bility, mildness, and prospective application to pharmaceuti-
cals and medicine [25]. However, few studies have explored
the interaction mechanism and influence factors of the zwit-
terionic/amino acid surfactant mixture system.
In this paper, we investigate the synergistic effect of the
zwitterionic surfactant CAPB and amino acid surfactant
SLS. The mixtures were characterized by a series of meas-
urements, including surface tension, rheological properties,
dynamic light scattering (DLS), and transmission electron
microscopy (TEM). The CAPB/SLS mixed system exhibits
a synergistic effect in the enhancement of surface activity. In
addition, the formation mechanism and rheological proper-
ties of the wormlike micelles were systematically investi-
gated. The results can give reference to oilfield fracturing
fluids, the pharmaceutical industry [12], and the formulation
of household detergents [26].
Materials and Methods
Materials
CAPB (active substance 30%) was provided by the Procter
& Gamble Research and Development Department, Bei-
jing, China, and SLS (active substance 30%) was supplied
by Clariant Chemicals (China) Ltd. Sodium chloride and
citric acid were obtained from Tianjin Experiment Reagent
Co. Ltd. of China. Ultrapure water was used for solution
preparation. All reagents and solvents were used as received
without further purification.
Sample Preparation
Mixed surfactant solutions with different mole fractions
( X1 = CCAPB ∕(CCAPB + CSLS ) ) were prepared by mixing
the corresponding surfactants and stirring until the solutions
were well mixed. Using citric acid, we adjusted the pH values
of the samples for the rheological tests. The total surfactant
13
H. Wei et al.
concentration was kept at 600 mmol/L, as is widely used in
cleaning products. The addition of corresponding NaCl to
the samples was made to eliminate the error caused by the
presence of NaCl in the raw material [26]. All samples were
mixed for 24 h prior to conducting the surface tension test,
and were held for 1 week prior to rheological test to ensure
that the system had reached equilibrium.
Surface Tension Measurement
The surface tensions of the samples were obtained using
a surface tension meter (QBYZ-1) and the platinum plate
method at (298.15 ± 0.1) K. The pH values of the solutions
were maintained at 6.95 ± 0.05. To calibrate the instrument,
we used the surface tension value of ultrapure water of
72 mN/m . The platinum was washed with ultrapure water
and then burned under an alcohol lamp before each meas-
urement. All the samples were measured repeatedly until
the difference between two values was less than 0.2 mN/m.
Rheological Measurements
The static viscosities of the samples were determined using
a DV2T Viscometer (Brookfield Engineering Laboratories,
USA) with rotor No. 95. Except when measuring the rheo-
logical properties at different temperatures, the rheological
properties of the samples were measured at (25 ± 0.1) °C
with a Kinexus Lab + rheometer (Malvern Instrument, UK).
All measurements were performed using plate geometry (40-
mm diameter) with a sample thickness of 0.1 mm in the
middle of the sensor. The viscosity 𝜂 of each sample was
obtained by steady-state shear measurement, and the shear
rate ranged from 0.1 to 100 s−1. The elastic modulus G′ and
the viscous modulus G′′ of the samples were obtained by a
dynamic strain frequency test with a frequency range from
0.1 to 30 Hz under a certain strain (ε = 0.01).
DLS Measurement
DLS measurements were performed using a Wyatt Nanostar
instrument. The temperature was maintained at 298.15 K
by a temperature controller with an accuracy of ± 0.1 K.
DLS measurements require a solution with high purity, so all
samples were passed through a 0.45𝜇m filter before testing.
TEM Observation
To observe the aggregate morphologies, we used the negative
staining method (with sodium phosphotungstate solution) for
the TEM with a JOEL JEM-1200EX (Japan). The sample was
spread on a copper grid and dyed with a metal salt so that the
entire grid was covered with a layer of heavy metal salt. No
dye was deposited where particles were protruding.
Synergistic Effect of Cocamidopropyl Betaine and Sodium Lauroyl Sarcosinate

Results and Discussion To explore the properties of mixed micelles, we used a

Surface Properties of Individual Surfactants
and CAPB/SLS Mixed Systems
Surface Tension Measurements
The critical micelle concentration (CMC) and other surface
properties of the pure surfactants and CAPB/SLS mixtures
were determined by surface tension measurements. We then
plotted the surface tension (𝛾 ) against the logarithm of the
concentration ( lg C ). The critical micelle concentration at
the breakpoint and the corresponding surface tension are
denoted as CMC and 𝛾CMC, respectively [27].
Figure 1 shows a plot of the surface tension ( 𝛾 ) versus
lg C , and Table 1 lists the critical micelle concentrations
and surface tensions of the mixed binary system at different
mole fractions. The CMC and 𝛾CMC values of the CAPB/
SLS mixed system are much lower than those of SLS. Upon
the addition of CAPB, the CMC and 𝛾CMC values of the
mixed binary system decreased, indicating excellent surface
activity.
70
60
50
γ (mN/m)
pseudo-phase separation model to calculate the ideal criti-
cal micelle concentration ( CMC∗ ) [28]. A lower CMC∗
value than the experimental CMC indicates the presence of
synergy in the systems. For binary surfactant mixtures, the
CMC∗ can be obtained using Eq. (1), and these values are
listed in Table 1:
1 X1 1 − X1
∗ = + (1)
CMC CMC1 CMC2
As shown in Table 1, the experimental CMC values are
smaller than the CMC∗ values due to the synergism in the
CAPB/SLS mixtures. In addition, the adsorption efficiency
factors pC20 are the negative logarithms of the surfactant
concentrations required to reduce the surface tension of
20 mN/m listed in Table 1. The pC20 values of the CAPB/
SLS mixed system are higher than that of SLS and greater
than 4.0, which also suggests that the CAPB/SLS mixed
system exhibits better surface activity than SLS [15].
Surfactant mixtures can generate mixed micelles, and
this usually depends on two factors. One is the interaction
between oppositely charged head groups of the surfactants,
and the other is the hydrophobic interaction between the
hydrocarbon tails. In this study, a pseudo-double chain sur-
factant formed at the tail due to the electrostatic interaction
SLS
between the cationic part of CAPB and the anionic part of
0.17 SLS. Stronger hydrophobic interaction facilitates the adsorp-
0.33 tion of surfactant molecules onto the interface, which results
0.5
in lower CMC and 𝛾CMC values [6].
0.67

0.83
CAPB Synergism of Surfactants
40

In non-ideal mixed solutions, there is a strong attraction

30
between molecules [12]. The interaction parameter 𝛽 estimates
the interaction between the head groups of different surfactants
20
according to the regular solution theory [6, 11]. The more
-5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 negative the 𝛽 value is, the stronger the mutual attraction of
lg C (mol/L) the surfactant molecules will be. The interaction parameters
of the mixed micelles (𝛽 m ) and the mixed monolayers (𝛽 𝜎 )
Fig. 1  Surface tension versus logarithm of the concentration of pure are obtained by measuring the CMC of the corresponding
and binary mixtures

Table 1  Values of CMC, CMC∗, No. Mole fraction of CMC (mmol/L) CMC∗ (mmol/L) 𝛾CMC (mN/m) pC20
𝛾CMC, and ­pC20 for various mole CAPB X1
fraction (X1) of CAPB/SLS
mixtures at 25 °C 1 0 4.476 23.9 3.54
2 0.17 0.479 0.706 20.7 4.31
3 0.33 0.204 0.394 19.1 4.57
4 0.50 0.134 0.268 21.4 4.81
5 0.67 0.164 0.203 19.6 5.11
6 0.83 0.141 0.165 19.7 4.87
7 1.00 0.138 27.1 5.09

13
 H. Wei et al.

surfactant mixture. The interaction between the CAPB/SLS where X1𝜎 is the mole fraction of CAPB in the mixed mon-
mixed binary system can be measured using Rubingh’s non- olayer; C1s , C2s , C12
s
are the concentrations of CAPB, SLS,
ideal mixing theory [11, 29]. According to this theory, the and the mixed binary system when the surface tension of the
critical micelle concentration of surfactant mixtures (C12
m
) can solution reaches 42 mN/m , respectively. The activity coef-
be obtained by Eq. (2): ficients of CAPB ( f1𝜎 ) and SLS ( f2𝜎 ) can be obtained from
the interaction parameter 𝛽 𝜎 of the mixed monolayer. Table 2
C = X1m f1m ⋅ C1m = X1 ⋅ C12
m
(2) lists the calculation results.
where C is the concentration of the surfactant CAPB; X1 As shown in Table 2, all the 𝛽 m and 𝛽 𝜎 values in the mixed
and X1m are the mole fractions of CAPB in solution and binary system are negative, which implies that the interac-
the mixed micelles, respectively; C1m and C12
m
are the CMC tions between CAPB and SLS in the mixed micelles and
values of the CAPB and mixed surfactants, respectively. mixed monolayer are stronger than that in the individual
The activity coefficients of CAPB ( f1m ) and SLS ( f2m ) are surfactant. 𝛽 𝜎 is more negative than 𝛽 m due to the greater
related to the interaction parameters, as given by the fol- difficulty in merging two hydrophobic groups into micelles
lowing equations: than that at the interface [31]. The 𝛽 m reaches the minimum
value of − 5.47 at X1 = 0.5, whereas 𝛽 𝜎 reaches a minimum
( )2
ln f1m = 𝛽 m 1 − X1m (3) of − 13.94 at X = 0.67 and the value of |𝛽 𝜎 | is greater than
| ( s s )| 1
|ln C1 ∕C2 |. This further proves that the surfactants CAPB
| |
( )2 and SLS have a strong mutual attraction in the mixed system
ln f2m = 𝛽 m X1m (4) [32]. According to the data in Table 2, the activity coeffi-
( ) ( ) cients ( f1m and f2m ) are both less than unity, which suggests
[S imn(c e f1m )] ∕ X1m C1m a n d f2m = C12
m m m
= X1 C12 1 − X1 ∕
non-ideal behavior between CAPB and SLS [11].
C2 1 − X1 , Eq. (3) can be written as follows [30]:
[ m ( )]
X1m2 ln C12 X1 ∕ C1m X1m Surface Activity Parameter
( )2 { m ( ) [ ( )]} = 1 (5)
1 − X1m ln C12 1 − X1 ∕ C2m 1 − X1m Surface tension measurements can also be used to determine
the accumulation of surfactant molecules at the air/water
where C2m is the CMC of the surfactant SLS. X1m is calculated
interface. Adsorption effectiveness is an essential factor in
using Eq. (5), and the interaction parameter 𝛽 m is calculated
determining the properties of emulsification, detergency,
using Eq. (6):
wetting, and foaming [6]. The maximum surface excess
[ m ]
ln C X1 ∕(C m m
X ) (𝛤max ) is estimated using the following Gibbs adsorption
12 1 1
𝛽m = ( )2 (6) equation [25, 28]:
1 − X1m ( )
1 d𝛾
Similarly, the interaction parameters of a single mixed layer 𝛤max = − ( ) (9)
2.303 2 − X 𝜎 RT d lg C T,P
are obtained using the Rubingh formula [4, 29]: 1

[ s ( )] where X1𝜎 is the mole fraction of CAPB in the mixed mon-

X1𝜎2 ln C12 X1 ∕ C1s X1𝜎
(7) olayer; R is the gas constant (R = 8.314 J/K mol); T is the
( )2 { s ( ) [ ( )]} = 1
1 − X1𝜎 ln C12 1 − X1 ∕ C2s 1 − X1𝜎 absolute temperature (T = 298.15 K); C is the concentration
of the surfactant; and d𝛾∕d lg C is the slope of the surface
[ s ( )] tension isotherm (temperature and pressure remain con-
ln C12 X1 ∕ C1s X1𝜎
𝜎 stant). With the following equation, the value of 𝛤max can
𝛽 = ( )2 (8)
1 − X1𝜎 be used to calculate the minimum area Amin occupied by
each adsorbed molecule (where NA is the Avogadro constant)
[25]:

Table 2  Interaction No. X1 X1m X1𝜎 𝛽m 𝛽𝜎 f1m f1𝜎 f2m f2𝜎

compositions ( X1 ), interaction
parameters (𝛽 ), and activity 1 0.17 0.713 0.585 − 2.30 − 9.19 0.827 0.205 0.310 0.043
coefficients ( f ) for the binary
2 0.33 0.710 0.609 − 4.46 − 10.65 0.687 0.197 0.105 0.019
mixture of CAPB/SLS systems
at 25 °C 3 0.50 0.728 0.624 − 5.47 − 12.00 0.667 0.183 0.055 0.009
4 0.67 0.855 0.631 − 3.40 − 13.94 0.931 0.150 0.083 0.004
5 0.83 0.889 0.671 − 3.83 − 12.75 0.954 0.251 0.049 0.003

13
Synergistic Effect of Cocamidopropyl Betaine and Sodium Lauroyl Sarcosinate

1 or rod-shaped micelles 0.33 ≤ P ≤ 0.50 . When P is close

Amin =
𝛤max NA
Table 3 lists the surface parameter values 𝛤max and Amin.
The higher 𝛤max value and lower Amin value in the mixed
binary system, as compared to those of the pure surfactant,
suggest that the molecules on the surface of the mixed system
are arranged more closely [12]. This is because the mutual
attraction of the positive and negative charges of the sur-
factants promotes the adsorption process on the surface of the
CAPB/SLS systems. The charge of the surfactant molecules
in the formed surface adsorption layer is freely neutralized,
and a double electric layer no longer exists on the surface.
No repulsion occurs between the surfactants, but there is an
electrostatic attraction. As a result, the hydrophobic groups are
arranged more tightly, which means they exhibit an excellent
ability to reduce surface tension.
The morphology of the ordered molecular assembly
depends on the geometry of the surfactant, and particularly on
the relative size of the cross-sectional areas of the hydrophilic
and hydrophobic groups in solution. Isrealachvili et al. [27, 33]
defined this property as the packing parameter P:
V
P=
Alc
(10) to 0.50, the curvature at the top of the micelle molecule is
large. This curvature will spontaneously reduce the number
at the top due to the higher energy, which will result in the
growth of cylindrical micelles into flexible long wormlike
micelles. Table 3 shows that the P value of SLS is less than
0.33, which indicates the formation of spherical micelles.
The significantly increasing P value in the mixed system
suggests the formation of rod-shaped micelles, which is
consistent with the TEM result. Another critical parameter
signifies the maximum reduction in surface tension 𝜋CMC ,
which is called the surface pressure. The larger 𝜋CMC values
obtained indicate that the surface activities of the mixtures
are superior to those of the individual surfactants.
Based on the above results that confirm the electrostatic
attraction between CAPB and SLS, this attraction leads to
the formation of rod-like micelles. As the concentration of
the surfactant is increased further, wormlike micelles appear.
The formation of wormlike micelles and their rheological
properties are detailed in the next section.
Influencing Factors on Rheological Properties
(11) Theory

where A is the area of the head group; and V and lc are the
critical volume and length of the hydrophobic chain, respec-
tively, obtained from the Cn number of carbon atoms in the
saturated hydrocarbon chain, according to the formulas of
Tanford [17, 34]:
( )
lc = 0.154 + 0.1265Cn nm (12)
( )
V = 0.0274 + 0.0269Cn nm3
The value of P relates to the shape of the surfactant mol-
ecules and aggregates. Theory suggests that for an ellipti-
cal or spherical micelle P ≤ 0.33, and for larger columnar
The rheological properties of the wormlike micelles in
semi-dilute regimes are usually determined using the Cates’
model [35]. In this model, relaxation arises from the sys-
tem’s internal properties in two phases: (1) reptation, which
denotes the reptile-like motion of the micelle [2], and (2)
reversible scission, which is the ability of the micelles to
break and reform. These two phases take place on two time
scales, the reptation time 𝜏r and breaking time 𝜏b. Maxwell-
(13) type behavior can be observed when 𝜏b ≪ 𝜏r [36, 37]. Based
on this, Cates and Candau proposed a model for predicting
a single relaxation time 𝜏R [3]:
( )0.5
𝜏R ≃ 𝜏b × 𝜏r (14)

In a semi-dilute regime, flexible micelles entangle to form

Table 3  Maximum surface excess (𝛤max), the minimum area a network much like those of polymers [38]. The modulus of
( Amin), packing parameter (P), and interfacial parameter (𝜋CMC) at
Maxwell’s viscoelastic fluid obeys the following relations [3]:
25 °C
No. Mole 𝛤max Amin ­(nm2) P 𝜋CMC (mN/m) 𝜔2 𝜏R2
fraction of ­(10−6 G� = G0 (15)
CAPB X1 mol·m2)
𝜔2 𝜏R2 + 1

1 0 2.08 0.800 0.261 48.1 𝜔𝜏R

2 0.17 3.90 0.426 0.491 51.3 G�� = G0 (16)
𝜔2 𝜏R2 +1
3 0.33 4.72 0.352 0.595 52.9
4 0.50 4.16 0.399 0.524 50.6 where G′ is the storage modulus (elastic modulus); G′′ is the
5 0.67 3.21 0.517 0.404 52.4 loss modulus (viscous modulus); 𝜔 is the oscillation fre-
6 0.83 4.18 0.397 0.526 52.3 quency; G0 is the elastic modulus extended to infinite fre-
7 1.00 3.65 0.455 0.460 44.9 quency (plateau modulus); and 𝜏R is the relaxation time of

13

the system. The critical modulus G∗ and the critical angular
frequency 𝜔∗ are obtained from the intersection of the G′ and
G′′ curves. The plateau modulus G0 and relaxation time 𝜏R
can be calculated using the following equations:
G0 = 2G∗ (17)
1
𝜏R = (18)
𝜔∗
𝜏R is proportional to the average contour length of the
micelles [17]. G0 is proportional to the number density of
the entanglement points in the micellar system [3], so it
can be used to describe the network structure. The zero-
frequency viscosity 𝜂𝜔 = 0, complex viscosity |𝜂 ∗ |, and the
relevant length 𝜉 , which can be estimated to characterize the
mesh size of the transient micelle network, are calculated by
Eqs. (19)–(21) [36].
𝜂𝜔 = 0 = G0 ∗ 𝜏R (19)
( )1∕2
|𝜂 ∗ | = G��2 + G2 ∕𝜔 (20)
( )1∕3
kB T
𝜉≈ (21)
G0
The Maxwell model is usually obtained by constructing a
Cole–Cole plot (G′′ vs. G′). For a Maxwellian fluid, the plot
is a semicircle with the center at (G0 ∕2, 0) and a radius of
G0 ∕2 [36]. However, the rheological behavior of wormlike
micelles deviates from the Maxwell model at high frequen-
cies, as manifested by an upturn in G′′, which is attributed to
a transition of the relaxation mode from slower reptation to
breathing or Rouse modes [2, 39]. The existence of worm-
like micelles can be further confirmed by TEM.
Effect of the Mole Fraction of CAPB/SLS
The steady shear rate–viscosity curves for the CAPB/SLS
system with X1 = 0.33, 0.42, 0.5, 0.58, and 0.67 (25 °C,
CT = 600 mmol/L, pH 4.7) are shown in Fig. 2. The viscos-
ity curves of the CAPB/SLS system with X1 = 0.33 and 0.67
are independent of the shear rate and exhibit typical New-
tonian fluid behavior. However, for the viscosity curves of
X1= 0.42, 0.5, and 0.58, a viscosity plateau appears at a low
shear rate and then shear-thinning behavior occurs at a high
shear rate. This is typical of non-Newtonian fluid behavior
and evidence of the formation of wormlike micelles [17].
With increases in the mole fraction, the one-dimensional
micelles begin to entangle with each other, which leads to a
considerable increase in viscosity [2]. As shown in Fig. 2,
the maximum viscosity of the solution occurred at X1 = 0.5,
13
H. Wei et al.
0.33
0.42
0.5
10 0.58
0.67
Viscosity (Pa⋅s)
1
0.1
0.1 1 10 100
Shear rate (s–1)
Fig. 2  Effect of CAPB mole fraction on the steady shear viscosity
rheological of the CAPB/SLS system (CT = 600 mmol/L, pH = 4.7) at
25 °C
which suggests that a micelle structure was easily formed by
the interaction of electricity and hydrophobicity [6].
In the CAPB/SLS system, the pH of the solution remained
at 4.7. The zwitterionic surfactant CPAB is known to behave
like a cation to attract the anionic surfactant. When the mole
fraction is either too low or high, the net charge in the mixed
micelles cannot be completely neutralized, which results in
lower viscosity. For X1 = 0.5, the net charge of the mixed
micelles was completely neutralized, and the electrostatic
repulsive force was weakened. These factors contributed to
the micellar growth and the formation of a classical linear
micelle network, as manifested by a significant increase in
viscosity. As X1 was further increased, the main zwitterionic
CAPB may have impeded the close packing of the surfactant
molecules, leading to a decrease in the zero shear viscosity.
Figure 3 also shows that the zero shear viscosity 𝜂0 of
the CAPB/SLS system (X1 = 0.5) is similar to the complex
viscosity |𝜂 ∗ |, which conforms to the Cox–Merz rule [40].
The zero shear viscosity η0 was obtained by extrapolating
the viscosity curve of the platform to a zero shear rate [17].
The 𝜂0 value is slightly higher than that of |𝜂 ∗ |, which indi-
cates that the wormlike micelles in the CAPB/SLS system
are more stable.
Effect of pH
The rheological behavior of the CAPB/SLS mixed system
also depends on the pH of the solution. Figure 4 shows the
effect of pH on the static viscosity of CAPB/SLS mixtures,
in which we can see that the viscosity increased initially
and then decreased dramatically with increases in pH, which
suggests a pH dependence of the structural transformation
of the mixed micelles. Based on this result, we selected the
Synergistic Effect of Cocamidopropyl Betaine and Sodium Lauroyl Sarcosinate

11
10 η (a) 10
9 |η* |
8
7

Viscosity (Pa⋅s)
6
Viscosity (Pa⋅s)

4 1

3 pH=5.0
pH=4.9
pH=4.8
pH=4.7
pH=4.6
2
pH=4.5
0.1
0.1 1 10 100
0.1 1 10 100 -1
Shear rate (s )
Frequency (Hz)
(b)
Fig. 3  Zero shear viscosity 𝜂0 and complex viscosity |𝜂 ∗ | of the
CAPB/SLS system

G′,G″ (Pa)
10 100
pH=4.9 G′
pH=4.9 G″
pH=4.7 G′
pH=4.7 G″
pH=4.5 G′
η (Pa⋅s)

1
pH=4.5 G″
10 100
Frequency (Hz)

0.1 (c) 350

pH=4.7
300 Theoretical curve
4.0 4.5 5.0 5.5 6.0 6.5 7.0
250
pH
G″(Pa)

200
Fig. 4  Static viscosity curve of CAPB/SLS mixtures for different pH
values 150

100

pH range (pH = 4.5–5.0) with the largest viscosity change for 50

further investigation of the rheological properties.
Figure 5a shows the steady-state shear viscosity curves
of the CAPB/SLS system at different pH values. We can
see that most samples exhibited shear thinning due to the
destruction of the reticulated micelles and the arrange-
ment in the shear direction at high shear rates. The maxi-
mum value of 𝜂0 occurred at pH = 4.7. The viscosity of the
system (pH < 4.7) was significantly decreased due to the
reduced solubility of SLS under acidic conditions. At the
same time, the pH of the solution influenced the proper-
ties of the zwitterionic surfactant in solution. CAPB was
unable to effectively attract the anionic surfactant SLS at
high pH. However, the electrostatic attraction between
the anionic group of SLS and cationic part of CAPB can
induce the surfactant molecules to form wormlike micelles
0 100 200 300 400 500
G′ (Pa)
Fig. 5  Effect of pH on the steady and dynamic rheological properties
of the CAPB/SLS system (CT = 600 mmol/L, pH = 4.7) at 25 °C. a
Steady shear viscosity curve, b elastic modulus G′ and viscous modu-
lus G′′ as a function of frequency, c Cole–Cole plot of the wormlike
micelles (solid line is the theoretical curve of the Maxwell model)
at a certain pH, as manifested by the enhanced viscosity
[17, 41].
Figure 5b and Fig. S1 show the dynamic viscoelastic prop-
erties of the CAPB/SLS system. At low frequencies, G′ < G′′,
and the system exhibits liquid-like behavior, whereas at high
frequencies, G′ > G′′, and the system behaves like a solid.

13
 H. Wei et al.

Table 4 summarizes the rheological parameters of the CAPB/
SLS system, from which we can see that as the pH decreased,
𝜏R and 𝜂0 increased initially and reached a peak value at
pH = 4.7, which indicates that the system with higher viscos-
ity needs a longer relaxation time to reach equilibrium [17].
Since 𝜏R is directly proportional to the average contour length
of the micelles, surfactant molecules form longer micelles due
to a synergistic effect. The increase in the G0 value implies
that the density of the entanglement points increased, whereas
ξ (equivalent to the network size) decreased. As the pH con-
tinued to decrease, the solubility of SLS decreased and the
change trend of these parameters was in the opposite direc-
tion. In addition, the 𝜂𝜔 = 0 determined by G0 and 𝜏R are in
good agreement with 𝜂0. The above results describe the for-
mation of wormlike micelles in the CAPB/SLS system and
its rheological properties at different pH values.
As shown in Fig. 5c and Fig. S2, in the Cole–Cole plot
of G′′ versus G′ (pH = 4.7) the Maxwellian fluid feature at
a low-frequency range is semicircular in shape. There is
a deviation from the semicircular line at high frequency,
however, which is due to the relaxation time. This deviation
depends not only on diffusion, but also on the dissociation
and recombination of the surfactant aggregates. A higher
viscosity of the solution leads to slower relaxation of the
structure and a longer relaxation time [3].
Effect of Temperature
Temperature is also an essential factor affecting the struc-
ture and rheological behavior of wormlike micelles [28]. We
studied the stable and dynamic rheological properties of the
CAPB/SLS system (CT = 600 mmol/L, X1 = 0.5, pH = 4.7) at
a temperature range from 15 to 35 °C, as shown in Fig. 6a.
In the plot of 𝜂0 versus 1/T in Fig. 7, the 𝜂0 value decreases
exponentially with increasing temperature, which is in
accordance with the Arrhenius equation [42, 43], as follows:
Ea
𝜂0 = AG0 e RT (22)
where Ea is the flow activation energy ( J∕mol); and A is the
pre-factor. From Fig. 7, Ea is calculated to be 85.9 kJ/mol ,
which describes a reversible equilibrium and end-cap energy
[17].
We also investigated the dynamic rheological properties
at temperatures ranging from 15 to 35 °C. Figure 6b shows
the dynamic properties (G′, G′′) of the samples, and Fig. 6c
shows the Cole–Cole plots. We can see that the system grad-
ually deviated from Maxwellian behavior with increases in
temperature, with 𝜏R and 1∕T exhibiting an exponential func-
tion relationship described by Arrhenius’ law [43]:
Ea
𝜏R = Ae RT (23)
Ea denotes the energy required for a single micelle to move
to the surrounding micelles in reversible scission [3, 17].
The value of Ea , as calculated from the curve of 𝜏R versus
1/T, is 93.5 kJ∕mol , which is close to the value obtained
from the curve of 𝜂0 versus 1/T. The exponential decrease in
𝜏R indicates a decrease in the contour length of the worm-
like micelles with increasing temperature. Furthermore, the
effect of temperature on the micelles can be explained by
the difference between the branching and end-cap energies
of the micelles [17], which is also a cause of the viscosity
decay in the solution.
DLS Measurements and TEM Observation
Using DLS, we determined the average hydrodynamic radius
(Rn) of the aggregates according to the Stokes–Stein equa-
tion. Figure 8 and Fig. S3 show size distribution histograms
of the aggregates at different molar fractions of the CAPB/
SLS mixture (concentrations of 3 mmol/L and 100 mmol/L).
As shown in Fig. 8, the pure CAPB and SLS have just a
single dimension. The Rn of SLS is distributed from 10 to
100 nm, and the Rn of CAPB ranges from 1 nm to 10 nm.
A bimodal or trimodal distribution can be observed in the
mixed system, which indicates the coexistence of multiple
aggregates when X1 = 0.17–0.83. The electrostatic attraction
of CAPB and SLS induces the surfactants to form larger
aggregates 1000 nm in size, which is an indicator of the
formation of rod-like micelles. The increase in the hydrody-
namic radius of these large aggregates suggests synergistic
growth of the micelles [12, 37].
Figure 9 shows the morphology of aggregates, which
was visualized by a negatively stained TEM micrograph.
The micrograph of the CAPB/SLS system at X 1 = 0.5,

Table 4  Rheological parameters No. pH G0 (Pa) 𝜔∗ (rad/s) 𝜏R ­(10−2 s) 𝜉 (nm) 𝜂𝜔 = 0 (Pa s) 𝜂0 (Pa s)
of CAPB/SLS system with the
variation in pH 1 5.0 138.4 125.5 0.7966 30.98 1.102 0.777
2 4.9 327.7 83.50 1.1980 23.24 3.925 4.249
3 4.8 401.2 53.34 1.8750 21.73 7.522 7.726
4 4.7 449.0 48.02 2.0830 20.93 9.351 8.930
5 4.6 598.4 114.3 0.8750 19.02 5.236 5.283
6 4.5 173.4 154.9 0.6456 28.74 1.120 0.541

13
Synergistic Effect of Cocamidopropyl Betaine and Sodium Lauroyl Sarcosinate

100
(a) 15 °C
20 °C
25 °C 10
30 °C
35 °C
Viscosity (Pa⋅s)

η0 (Pa⋅s), τM (s)
10
1

0.1

0.01 η0
τΜ
1
0.1 1 10 100 0.001
0.00325 0.0033 0.00335 0.00341 0.00347
-1
Shear rate (s ) 1/T (K-1)

(b)
Fig. 7  Profile of 𝜂0 and 𝜏R in the CAPB/SLS system
(CT = 600 mmol/L, X1 = 0.5, pH = 4.7)

15 °C G′
G′, G″ (Pa)

100 15 °C G″
20 °C G′
20 °C G″
25 °C G′
25 °C G″
30 °C G′
30 °C G″
35 °C G′
35 °C G″
10
1 10
Frequency (Hz)

(c) 400
350

300

250
G″ (Pa)

200

150
15 °C
100
20 °C
50 25 °C
30 °C
0 35 °C
-50
0 100 200 300 400 500 600 700
G′ (Pa)

Fig. 6  Effect of temperature on the steady and dynamic rheological

properties of the CAPB/SLS system. a Steady shear viscosity curve,
b elastic modulus G′ and viscous modulus G′′ as a function of fre-
quency Hz, c Cole–Cole plots of wormlike micelles at different tem-
peratures (solid lines are the theoretical curves of the Maxwell model)

CT = 3 mmol/L confirms the existence of wormlike micelles

with lengths of 200–300 nm. It is clear that the threadlike
micelles are entangled together, which is consistent with
the DLS results. Figure S4 also shows a visualization of the
micelle morphology.
Fig. 8  Size distribution histograms of aggregates formed in the mixed
system and the individual surfactant (CT = 3 mmol/L)

13

Fig. 9  Negatively stained TEM micrograph of CAPB/SLS mixture at
3 mmol/L
Conclusions
In this work, the interaction between CAPB and SLS was
investigated for the first time. CAPB/SLS mixed systems
were found to exhibit lower CMC values and better surface
activities than individual surfactants. The negative values
of the interaction parameter 𝛽 proved the presence of elec-
trostatic attraction in all the binary mixtures. Stable and
dynamic viscoelastic measurements of the CAPB/SLS sys-
tem were obtained. In addition, the effects of mole fraction,
pH, and temperature on the rheological properties of the
system were found to cause the structural transformation of
wormlike micelles. The contour length of the micelles and
the number density of the entanglement points were found
to have a major influence on the viscosity of the micellar
system. The rheological properties of the mixed system fit
well with the Maxwell model at low frequency. The study
results show that the molecular network of the micelles was
strongest at CT = 600 mmol/L, X1 = 0.5, and pH = 4.7. The
formation of long wormlike micelles in the CAPB/SLS mix-
ture was also observed via DLS and TEM.
The above experimental results contribute to the under-
standing of the surfactant interactions and rheological prop-
erties of wormlike micelles. Furthermore, better surface
activity of the compound system is of great significance for
personal care products and household detergents.
Acknowledgements The authors gratefully acknowledge P&G Tech-
nology (Beijing) Co., Ltd., for providing technical support.
References
1. Wydro P, Paluch M (2005) A study of the interaction of dode-
cyl sulfobetaine with cationic and anionic surfactant in mixed
13
H. Wei et al.
micelles and monolayers at the air/water interface. J Colloid
Interface Sci 286(1):387–391
2. Shrestha RG, Shrestha LK, Aramaki K (2007) Formation of
wormlike micelle in a mixed amino-acid based anionic sur-
factant and cationic surfactant systems. J Colloid Interface Sci
311(1):276–284
3. Różańska S (2015) Rheology of wormlike micelles in mixed
solutions of cocoamidopropyl betaine and sodium dodecylb-
enzenesulfonate. Colloids Surf A Physicochem Eng Asp
482:394–402
4. Bergström M (2001) Synergistic effects in mixtures of an ani-
onic and a cationic surfactant. Langmuir 17(4):993–998. https​
://doi.org/10.1021/la000​814t
5. Kanoje B, Padshala S, Parikh J et al (2018) Synergism and
aggregation behaviour in an aqueous binary mixture of cati-
onic–zwitterionic surfactants: physico-chemical characteriza-
tion with molecular simulation approach. Phys Chem Chem
Phys 20(1):670–681. https​://doi.org/10.1039/c7cp0​5917e​
6. Wang XQ, Wang RT, Zheng Y et al (2013) Interaction between
zwitterionic surface activity ionic liquid and anionic surfactant:
­Na+-driven wormlike micelles. J Phys Chem B 117(6):1886–1895
7. Wei HY, Feng BH, Zhao GZ et al (2018) Effect of non-reactive
powder particle properties on dry agglomeration in a high shear
mixer. Trans Tianjin Univ 24:442–452. https​://doi.org/10.1021/
jp308​016a
8. Prajapati RR, Bhagwat SS (2012) Effect of foam boosters on the
micellization and adsorption of sodium dodecyl sulfate. J Chem
Eng Data 57(12):3644–3650. https​://doi.org/10.1021/je300​8155
9. Danov KD, Kralchevska SD, Kralchevsky PA et al (2004)
Mixed solutions of anionic and zwitterionic surfactant (betaine):
surface-tension isotherms, adsorption, and relaxation kinetics.
Langmuir 20(13):5445–5453. https​://doi.org/10.1021/la049​576i
10. Li YP, Lv W, Cao XL et al (2014) Study of the synergistic
effect of sodium dodecyl sulfate and betaine at the air/water
and oil/water interfaces. Acta Chim Sin 72(5):615. https​://doi.
org/10.6023/a1402​0124
11. Ghosh S, Khatua D, Dey J (2011) Interaction between zwit-
terionic and anionic surfactants: spontaneous formation of
zwitanionic vesicles. Langmuir 27(9):5184–5192. https​://doi.
org/10.1021/la104​0147
12. Vashishat R, Chabba S, Mahajan RK (2016) Effect of surfactant
head group on micellization and morphological transitions in
drug-surfactant catanionic mixture: a multi-technique approach.
Colloids Surf A Physicochem Eng Asp 498:206–217
13. Roy S, Nayak RR, Dey J (2006) Stable vesicle formation
through intra- and inter-chain aggregation of poly[sodium
N-(11-acrylamidoundecanoyl)-L-valinate] in aqueous solution.
Colloids Surf A Physicochem Eng Asp 290(1–3):62–69. https​
://doi.org/10.1016/j.colsu​r fa.2006.05.002
14. Lopez-Diaz D, Sarmiento-Gomez E, Garza C et al (2010) A
rheological study in the dilute regime of the worm-micelle fluid
made of zwitterionic surfactant (TDPS), anionic surfactant
(SDS), and brine. J Colloid Interface Sci 348(1):152–158. https​
://doi.org/10.1016/j.jcis.2010.03.038
15. Ghosh S, Dey J (2011) Interaction of sodium N-lauroylsarcosi-
nate with N-alkylpyridinium chloride surfactants: spontaneous
formation of pH-responsive, stable vesicles in aqueous mix-
tures. J Colloid Interface Sci 358(1):208–216
16. Bajpai AK, Shukla SK, Bhanu S et al (2008) Responsive poly-
mers in controlled drug delivery. Prog Polym Sci 33(11):1088–
1118. https​://doi.org/10.1016/j.progp​olyms​ci.2008.07.005
17. Zhou M, Li SS, Zhang Z et al (2016) Synthesis of oligomer
betaine surfactant (DDTPA) and rheological properties of worm-
like micellar solution system. J Taiwan Inst Chem Eng 66:1–11.
https​://doi.org/10.1016/j.jtice​.2016.05.013
Synergistic Effect of Cocamidopropyl Betaine and Sodium Lauroyl Sarcosinate
18. Chu ZL, Dreiss CA, Feng YJ (2013) Smart wormlike micelles.
Chem Soc Rev 42(17):7174–7203
19. Xv Y, Wang F, Hou QF et al (2019) Strategy for synthesizing
novel acetamidines as ­CO2-triggered switchable surfactants
via acetimidates. Trans Tianjin Univ 25:237–244. https​://doi.
org/10.1039/c3cs3​5490c​
20. Stukan MR, Boek ES, Padding JT et al (2008) Flow of worm-
like micelles in an expansion–contraction geometry. Soft Matter
4(4):870–879. https​://doi.org/10.1039/b7134​98c
21. Müller T, Krämer C, Pritzel C et al (2018) Influence of cocamido-
propyl betaine on the formation and carbonation of portlandite—a
microscopy study. Constr Build Mater 163:793–797
22. Abdel-Rahem RA, Reger M, Hloucha M et al (2014) Rheology
of aqueous solutions containing SLES, CAPB, and microemul-
sion: influence of cosurfactant and salt. J Dispers Sci Technol
35(1):64–75
23. Shao WY, Zhang JY, Wang K et al (2018) Cocamidopropyl
betaine-assisted foam separation of freshwater microalgae
Desmodesmus brasiliensis. Biochem Eng J 140:38–46. https​://
doi.org/10.1016/j.bej.2018.09.006
24. Erfani A, Flynn NH, Ramsey JD et al (2019) Increasing protein
stability by association with zwitterionic amphiphile cocamido-
propyl betaine. J Mol Liq 295:111631. https​://doi.org/10.1016/j.
molli​q.2019.11163​1
25. Bajani D, Gharai D, Dey J (2018) A comparison of the self-assem-
bly behaviour of sodium N-lauroyl sarcosinate and sodium N-lau-
royl glycinate surfactants in aqueous and aqueo-organic media.
J Colloid Interface Sci 529:314–324. https​://doi.org/10.1016/j.
jcis.2018.06.026
26. Staszak K, Wieczorek D, Michocka K (2015) Effect of sodium
chloride on the surface and wetting properties of aqueous solu-
tions of cocamidopropyl betaine. J Surfact Deterg 18(2):321–328.
https​://doi.org/10.1007/s1174​3-014-1644-8
27. Patra N, Ray D, Aswal VK et al (2018) Exploring physicochemi-
cal interactions of different salts with sodium N-dodecanoyl sar-
cosinate in aqueous solution. ACS Omega 3(8):9256–9266. https​
://doi.org/10.1021/acsom​ega.8b007​18
28. Sehgal P, Doe H, Wimmer R et al (2008) Mixed monolayer
and micelle formation of cationic and zwitterionic surfactant
of identical hydrocarbon tail in an aqueous medium: interfacial
tension, fluorescence probe, dynamic light scattering, and vis-
cosity studies. J Dispers Sci Technol 29(3):327–334. https​://doi.
org/10.1080/01932​69070​17160​28
29. Rosen MJ (1989) Surfactants and interfacial phenomena. Wiley,
Hoboken
30. Mahajan RK, Sharma R (2011) Analysis of interfacial and micel-
lar behavior of sodium dioctyl sulphosuccinate salt (AOT) with
zwitterionic surfactants in aqueous media. J Colloid Interface Sci
363(1):275–283
31. Kabir-Ud-din SM, Dar AA (2009) Interaction of a cationic gemini
surfactant with conventional surfactants in the mixed micelle and
monolayer formation in aqueous medium. J Colloid Interface Sci
333(2):605–612
32. Geng T, Zhang CQ, Jiang YJ et al (2017) Synergistic effect of
binary mixtures contained newly cationic surfactant: interac-
tion, aggregation behaviors and application properties. J Mol Liq
232:36–44
33. Israelachvili JN, Mitchell DJ, Ninham BW (1976) Theory of self-
assembly of hydrocarbon amphiphiles into micelles and bilayers.
J Chem Soc Faraday Trans 2(72):1525. https​://doi.org/10.1039/
f2976​72015​25
34. Tanford C (1974) Structures in an aqueous world. (Book reviews:
the hydrophobic effect. formation of micelles and biological mem-
branes). Science 184(4136):559–560
35. Cates ME, Candau SJ (1990) Statics and dynamics of worm-like
surfactant micelles. J Phys Condens Matter 2(33):6869–6892.
https​://doi.org/10.1088/0953-8984/2/33/001
36. Georgieva GS, Anachkov SE, Lieberwirth I et al (2016) Synergis-
tic growth of giant wormlike micelles in ternary mixed surfactant
solutions: effect of octanoic acid. Langmuir 32(48):12885–12893.
https​://doi.org/10.1021/acs.langm​uir.6b039​55
37. Roy S, Dey J (2007) Effect of hydrogen-bonding interactions on the
self-assembly formation of sodium N-(11-acrylamidoundecanoyl)-
L-serinate, L-asparaginate, and L-glutaminate in aqueous solu-
tion. J Colloid Interface Sci 307(1):229–234
38. Wei HY, Lu JL, Gu C et al (2018) Visualization of wormlike
micelle fluid flow in a mixing tank. Trans Tianjin Univ 24(4):308–
317. https​://doi.org/10.1016/j.jcis.2006.11.014
39. Moore JE, McCoy TM, de Campo L et al (2018) Wormlike micelle
formation of novel alkyl-tri(ethylene glycol)-glucoside carbohy-
drate surfactants: structure–function relationships and rheology.
J Colloid Interface Sci 529:464–475. https​://doi.org/10.1016/j.
jcis.2018.05.060
40. Cox WP, Merz EH (1958) Correlation of dynamic and steady flow
viscosities. J Polym Sci 28(118):619–622. https:​ //doi.org/10.1002/
pol.1958.12028​11812​
41. López-Díaz D, García-Mateos I, Velázquez MM (2005) Syner-
gism in mixtures of zwitterionic and ionic surfactants. Colloids
Surf A Physicochem Eng Asp 270–271:153–162
42. Candau SJ, Hirsch E, Zana R et al (1988) Network properties of
semidilute aqueous KBr solutions of cetyltrimethylammonium
bromide. J Colloid Interface Sci 122:430–440
43. Raghavan SR, Kaler EW (2001) Highly viscoelastic wormlike
micellar solutions formed by cationic surfactants with long unsat-
urated tails. Langmuir 17(2):300–306. https​://doi.org/10.1021/
la000​7933
Hongyuan Wei received his Ph.D.
from The University of Man-
chester and works as a professor
in the Industrial Crystallization
Center of the School of Chemi-
cal Engineering, Tianjin Univer-
sity. His research interests are
industrial crystallization, fluid
mechanics, chemical safety and
green separation technology.
Leping Dang received her Ph.D.
from Tianjin University and
works as an associate researcher
in the industrial crystallization
center of the school of chemical
engineering, Tianjin University.
Her research fields are industrial
crystallization, pharmaceutical
crystallization, green separation
technology and chemical safety.
13