Journal of Molecular Liquids 198 (2014) 8493

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Rheological model for micelles in solution from molecular dynamics

E.O. Castrejn-Gonzlez a,, V.E. Mrquez Baos a, J.F. Javier Alvarado a, V. Rico-Ramrez a,
J. Castillo-Tejas b, H. Jimnez-Islas c
a
b
c

Departamento de Ingeniera Qumica, Instituto Tecnolgico de Celaya, Celaya Gto. 38010, Mexico
Facultad de Ciencias Bsicas, Ingeniera y Tecnologa, Universidad Autnoma de Tlaxcala, Apizaco Tlax., 90300, Mexico
Departamento de Ingeniera Bioqumica, Instituto Tecnolgico de Celaya, Celaya Gto. 38010, Mexico

a r t i c l e

i n f o

Article history:
Received 24 February 2014
Received in revised form 29 June 2014
Accepted 14 July 2014
Available online 23 July 2014
Keywords:
Rheology
Micelles
Structure factor
Molecular dynamics
Shear ow

a b s t r a c t
Non-equilibrium molecular dynamics was performed to determine the rheological behavior of micelles in
solution. Different concentrations of surfactants molecules immersed into two types of solvents were studied.
Three regions in the ow curve were obtained: i) A rst Newtonian plateau, ii) a second shear-thinning region
and iii) a third shear-thickening region. Data from ow curve were well tted to a proposed model based on
the CarreauYasuda equation. Molecular snapshots and static structure factor were determined to complement
the structure information. Results are in qualitative agreement with experimental data.
2014 Elsevier B.V. All rights reserved.

1. Introduction
An interesting topic for researchers [1] has recently emerged.
A complex uid is characterized by its microstructure and it is generally
measured through scattering techniques such as small angle light,
neutron, or X-ray scattering [2]. Colloids, liquid crystals, polymers and
micelles are some examples of complex uids [2,3]. In complex uids,
spontaneous formation of molecular aggregation can occur when a strong
asymmetry between the solute and solvent molecules is presented [4,5];
such as in the case of surfactants.
Surfactant molecules are amphiphilic, as they posses both hydrophilic heads and hydrophobic tails. When the amphiphilic molecule
concentration in aqueous solution is larger than a critical micelle
concentration (CMC) micellar aggregates are formed.
The shape of the aggregates depends on several factors such as:
the molecular interactions, the physical-chemistry conditions of the
solution, the temperature and, if it were the case, the ow conditions.
One of such self-assembled aggregates is known in the literature as
wormlike micelles [6].
Micellar solutions have been used as rheology modiers in paints,
detergents, pharmaceutical products, lubricants and emulsions where
properties of the uids are strictly controlled [7]. Also, micellar solutions
have been widely used in drying agrochemical products, ink-jet printing, reduction of turbulence resistance and enhanced oil recovery [8,9].

Corresponding author. Tel.: +52 461 6117575.

E-mail address: omar@iqcelaya.itc.mx (E.O. Castrejn-Gonzlez).

http://dx.doi.org/10.1016/j.molliq.2014.07.016
0167-7322/ 2014 Elsevier B.V. All rights reserved.

The rheological behavior of surfactants is a consequence of the

microstructure of micelles and scission-recombination kinetics.
Although several experimental studies have been developed [8,1012],
a full understanding of this mechanism remains elusive [13].
Due to the wide industrial and commercial application of the
micellar solutions, a detailed comprehension of the behavior at
different ow regions is required [14].
Molecular simulations have been an important tool to understand
the ow behavior of complex liquids. Particle based simulations of
wormlike micelles may be performed on many different lengths and
time scales, from the atomistic to the mesoscopic. To realistically simulate the rheology, one would ideally use an atomistic model (all-atoms)
or a model in which each amphiphilic molecule was individually represented by a properly coarse-grained version of it [15]. This simplication
can considerably reduce the compute time for a very long time scales.
In recent years, several surfactant models have been proposed
[1624] to reproduce the self-assembled aggregates; however,
rheological description of these systems is not widely understood.
Krguer and Makhlou [25] proposed the FENE-C (nitely extensible
nonlinear elastic, C for cut) potential to simulate the scission and recombination process. With the same potential mentioned above, Padding
and Boek [26] studied the inuence of the shear ow on ring formation
in a micellar solution; however, they did not observe shear-thickening,
which is actually encountered in experimental data [2729].
Castillo-Tejas et al. [30] studied wormlike micelles in systems
constituted by united atom model immersed in a LennardJones
solvent, where they found a shear-thickening behavior at high
shear rates; however, the study lacks structural information.

E.O. Castrejn-Gonzlez et al. / Journal of Molecular Liquids 198 (2014) 8493

The aim of this study is to increase the information about the

structure of micellar solutions under shear ow and to propose a new
rheological model to t the complex behavior of these systems.
2. Methodology
2.1. Model and simulation
A united atom model was used to describe the surfactant molecule;
the tail was considered as four hydrophobic sites with a size of ,
whereas the head was an hydrophilic site with size 41/3. Surfactant
molecules were immersed in two types of solvents, trying to reproduce
the qualitatively behavior of both water and oil. Each solvent particle
was considered as a site of size .
The truncated and shifted LennardJones (LJ) potential given by
Eq. (1) was used to model pair interactions between particles with
same afnity which include: oiloil, waterwater, tailtail, headhead,
waterhead, and oiltail interactions.
(
LJ

U ij

"
4

r ij

!12

r ij

!6 #
;

r ij r c

0;

r ij Nr c

the cut-off ratio for the solvent-solvent interaction was xed to

rc = 2.5. To reproduce the chemical bond between sites forming the
molecule, a harmonic potential is used:
 

2
U b r ij K rij ij

where K is an energy-level parameter, and ij is calculated using the

LorentzBerthelot combining rules given by ij = 0.5(ii + jj).
Repulsive potential (R) is given by:
R

U ij

1:05 ij
r ij

!9

2
0
v 4
0

0
0
0

3
0
05
0

where is the applied shear rate.

The whole set of variables are in reduced units; the relevant parameters
are: = 3, T = kBT/, U = U/, P = P 3/, t = t(/ 2m)1/2,

1=2

, and = 2/(m)1/2, where is the local density,

m= 2
U is the energy, P is the pressure tensor, is the viscosity and t is the
time. For simplicity, hereafter the asterisk notation will be omitted.
2.2. Structure factor
The structure factor S(k) is dened as the autocorrelation
function: [36]
Sk

pia F ia pia  v pia

p
;
Q

where subscripts i and a are used to distinguish molecules from

particles, respectively, and the dot notation means time derivative.
The symbols qia, pia, Fia, and mia represent the position, momentum
and force vectors and the mass of particle a in molecule i, respectively.
N is the total number of particles, T is the temperature, and kB is
the Boltzmann constant. Q, , p and represent the inertial mass,
coordinates, momenta and dimensionless time, respectively, of the
NosHoover thermostat. The velocity gradient tensor v in shear
ow is given by

pia
qia  v
mia

X X p2
ia
3NkB T;
mia
a
i

1
h i
N k k

where
:

The above potentials are implemented in LAMMPS (Large-scale

Atomic/Molecular Massively Parallel Simulator) [31]; parameters are
included in Table 1. Fig. 1 summarizes the particle interactions.
NEMD simulations in the NVT ensemble were performed using the
SLLOD equations of motion for a homogeneous shear ow [32], which is
equivalent to the p-SLLOD equations for planar Couette ow [33]. The
NosHoover thermostat [34,35] was applied to keep the temperature
constant. The equations of motion are:
qia

85

Q 3NkB T

N
X



exp ik  r j

is the Fourier transform of the microscopic (total) density and r j

denotes the position of particle j, with 1 j N. This equation,
along with the Euler's identity exp( ia) = cos(a) isin(a) allows
computing static structure factors from molecular simulation. The
minimum k vector for a box of length L for the N particle system
is (2/L) [37] and therefore, the components of the k vector are
restricted, due to periodic boundary conditions, to multiples of
(2/L). If k has only components x and y, then:
^ ky y
^ nx
k kx x

Table 1
Dimensionless variables and parameters used in the simulations.
Variable

Symbol

Value

Particle mass
Particle tail and solvents diameter
Particle head diameter
Energy
Density
Temperature
K constant
Maximum bond length

T
K
R0

1.0
1.0
41/3
1.0
0.84
1.35
30
1.5

10

j1

 
 
2
2
^ ny
^
x
y
L
L

11

where nx and ny are integer numbers.

The structure factor can be measured directly through radiation
scattering experiments; in particular, from Static Light Scattering
(SLS). This experimental technique has been a useful tool to elucidate
the molecular structure of materials. It has been used to determine
density uctuations of a system due to external light perturbation
with a wavelength of 2/k. In particular, the SLS has been widely used
to characterize micelles in solution [11,38,39]. The radius of gyration
Rg and the second virial coefcient B2 are some of properties that can
be obtained from SLS experiments.
In a dilute solution formed by np chains (np N N 1), with N sites per
molecule, the static structure factor, also called scattering function, for
a single molecule can be obtained from Eq. (12) [40]:
S1 k

N D
h

iE
1 X
exp ik  ri r j
N j;k1

12

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E.O. Castrejn-Gonzlez et al. / Journal of Molecular Liquids 198 (2014) 8493

Hydrophilic
Head

Hydrophobic
Tail

R
1/3

type 1
water like
L-J

L-J
R

L-J
R

L-J

L-J

L-J

type 2
oil like

Fig. 1. Particle interaction scheme. Red circles correspond to hydrophilic heads and blue circles correspond to hydrophobic tail beads in the surfactant molecules. Two types of solvent
are represented by light (1) and dark (2) circles being water like (W) and oil like (O), respectively. Interactions between tails and heads, oil like and water like, oil like and heads, and
water like and tail are represented by a repulsive potential (R) (see Eq. (1)). Interactions between related particles are represented by truncated and shifted the LennardJones potential
(Eq. (2)) whereas bonded chains are represented by a harmonic potential (Eq. (3)). (For interpretation of the references to color in this gure legend, the reader is referred to the web
version of this article.)

Fig. 2. Molecular snapshots of = 0.23 at slow shear rate for a) 0, b) 10, c) 50 and d) 70% of O solvent. Biggest (red) spheres correspond to heads; blue spheres represent the tails, gray and
brown spheres are W and O solvent particles, respectively. Micellar aggregates are well dened. (For interpretation of the references to color in this gure legend, the reader is referred to
the web version of this article.)

E.O. Castrejn-Gonzlez et al. / Journal of Molecular Liquids 198 (2014) 8493

87

S (k )

a)

b)

S (k )

kY ( 1 )

S (k )

S (k )

c)

d)
S (k )

kY ( 1 )

S (k )

k X ( 1 )

k X ( 1 )

Fig. 3. Static structure factor in XY plane projection for = 0.23 at zero shear rate for a) 0, b) 10, c) 50 and d) 70% of O solvent.

Fig. 4. Shear viscosity vs. shear rate for the 0.01 (), 0.02 (), 0.03 (), and 0.04 () solutions at a) 0%, b) 10%, c) 50% and d) 70% of O solvent, respectively. Proposed rheological model ts
well the simulated data in the whole shear rates region.

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E.O. Castrejn-Gonzlez et al. / Journal of Molecular Liquids 198 (2014) 8493

Table 2
Parameters of the modied CarreauYasuda model that ts simulation data.
Oil %

min

n1

n2

0%

1
2
3
4
1
2
3
4
1
2
3
4
1
2
3
4

0.8770
0.9580
1.0300
1.3200
0.9020
1.0070
1.0600
1.3500
0.9650
1.0020
1.0600
1.4200
0.9400
1.0000
1.1100
1.4000

0.5027
0.8900
1.1500
2.2800
0.7100
1.0700
1.5500
2.9900
0.7400
1.3000
1.2000
3.7320
0.7100
1.0700
1.6350
3.6500

0.0470
0.0789
0.0789
0.2000
0.0711
0.1000
0.1382
0.2700
0.0613
0.1000
0.1000
0.2680
0.0700
0.0700
0.1430
0.2630

0.1983
0.2308
0.2212
0.2489
0.2211
0.2306
0.2250
0.2550
0.2312
0.2196
0.2129
0.2483
0.2247
0.2039
0.2125
0.2328

0.0055
0.0091
0.0065
0.0085
0.0065
0.0071
0.0080
0.0105
0.0075
0.0095
0.0079
0.0130
0.0068
0.0075
0.0107
0.0100

2.2324
2.2921
2.4116
2.8041
2.2248
2.0060
2.2821
2.5890
1.6877
2.0030
2.2001
1.9555
1.8675
2.3427
2.5399
2.2977

3.6471
5.6154
3.5801
4.6986
3.9423
3.8298
4.1279
5.6273
5.1130
5.2340
3.9485
5.8000
3.2665
4.1853
5.7135
5.7849

0.2776
0.2187
0.2225
0.2485
0.2843
0.2892
0.2833
0.3006
0.2909
0.3073
0.3120
0.3383
0.2700
0.2915
0.3300
0.3497

2.0052
1.6810
1.7099
1.7273
1.9293
1.9310
1.9297
1.9427
1.9489
1.3346
1.3585
1.1314
1.9601
1.9829
2.6572
10.7768

10%

50%

70%

where k is the scattering vector which is the difference between the

scattered beam wave vector ks and the incident beam wave vector ko.
For nite concentrations, the interference between sites of neighboring
chains must be taken into account. In this case, the structure factor is
given by
Sk S1 k

N D
h

iE
np X
exp ik  r1i k2 j
:
N i; j1

13

The second term adds up the correlations between nearby

molecules 1 and 2. At low concentrations, however, the statistical

average for different molecules is mostly zero, and S(k) becomes

identical to S1(k).

2.3. Rheological model proposed

Complex rheological behavior is presented in various systems,
such as Newtonian, shear thinning and shear thickening simultaneous
effects which are presented in micellar solutions [30,41], colloids
and suspensions [4244] and some polymer solutions [45,46]; some
complex behaviors such as second shear thinning region are presented
in cellulose and ionic liquid mixtures [47,48]. The lack of rheological

Fig. 5. Snapshots for = 0.23 and 0% of O solvent particles for a) = 1, b) = 4, c) = 20 and d) = 100.

E.O. Castrejn-Gonzlez et al. / Journal of Molecular Liquids 198 (2014) 8493

S ( 0, k y

k y ( 1 )

S ( 0, k y

S ( kX , 0)

S ( kx , 0)

89

S ( 0, k y

k y ( 1 )

S ( 0, k Y )

S ( kX , 0)

S ( ky , 0)

kx ( 1 )

kx ( 1 )

Flow direction

Fig. 6. Static structure factor for = 0.23 and 0% of O solvent particles for a) = 1, b) = 4, c) = 20 and d) = 100.

models in the literature for representing, simultaneously, more than

two changes in the ow curve with only one equation, has been the motivation to propose a new rheological model. In fact, our model is
intended to t well experimental data even in the cases of four or ve
ow curve changes.
Considerations used to describe the shear behavior of the micellar
solutions that include shear-thickening and shear-thinning behavior
are based on a CarreauYasuda [49,50] model. It is well known that
the CarreauYasuda equation has proved to be an excellent model to
t the whole shear rate interval for polymer solutions with both regions,
Newtonian and Shear thinning [51]. The equation is given by:
0
h
  ip
1 2

14

where 0 is the zero shear rate viscosity, is a characteristic time

the shear rate and p is a numerical exponent. However,
constant, is
it is not possible to reproduce the whole shear behavior in micellar
solutions. We proposed the following model, where it is possible to
reproduce ve regions in the ow curve, such as rst Newtonian plateau, two shear thinning or shear thickening regions, intermediate
Newtonian region and a last Newtonian plateau at high shear rates:

0 in
in

 a n1 
 b m1
1 1
1 2

15

where 0 is the viscosity at rst Newtonian plateau, in is the

intermediate Newtonian viscosity, is the viscosity at last Newtonian
plateau; 1 and 2 are the relaxation times. If b 1=1 the rst Newtonian region is depicted, else if N1=2 , the last Newtonian plateau

is presented. Parameters a and b are used to describe the transitions

between constant viscosity and the shear thinning regions with a
power law behavior. Finally n and m parameters are the exponents
analogous to power law expressions. If Newtonian plateaus 0 and
are unknown, then these could be used as adjustable parameters.
2.4. Material functions
The pressure tensor P is given by a sum of site-site contributions:
2
3
1 4X pki pli 1 X X

r F 5
P kl
mi
V
2 i jNi kij lij
i

16

where Pkl is the pressure tensor component acting along l direction

through a normal plane to the k axis, pki and pli are the k and l components of the momentum of particle i and mi its associated mass. Furthermore, V is the system volume, rkij is the k-component of the scalar
distance rij, and Flij is the l-component of the force resulting from the interaction between particles i and j. The rst term of Eq. (16) represents
the kinetic contribution, and the second arises from pair interactions.
For the system studied here, the main contribution to pressure tensor
stems from the pair potentials.
The shear viscosity is dened by:
D

P xy

E
17

where Pxy is the average of the xy component of Pressure tensor over

the time in the production step.

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Fig. 7. Snapshots for = 0.23 and 10% of O solvent particles for a) = 1 (Newtonian region), b) = 4 (Shear-thinning region), c) = 10 (At the minimum shear viscosity) and d) = 60
(Shear-thickening region).

3. Results and discussion

Four surfactant concentrations were studied: 0.05, 0.10, 0.15 and
0.20; all of them were immersed into two types of solvent, W-like and
O-like; four proportions of O and W solvents were studied 0, 10, 50
and 70% of O solvent. The concentrations were calculated by Eq. (18):

N ch Lch
Nch Lch N S

18

where Nch is the number of surfactant molecules with a length Lch; NS is

constituted by two types of solvent, NS = SW + SO, where SW is the
number of water-like solvent sites and SO is the number of oil-like
solvent sites.
All of the systems were composed of 12, 000 sites at reduced
temperature and density of 1.35 and 0.66, respectively. To generate
different concentrations, we varied the number of surfactant molecules
Nch from 120 to 580.
Since a simple model potential was used, it was possible to develop
large simulations achieving to verify the micellar assemblies.
3.1. Equilibrium molecular dynamics
Molecular structures at equilibrium conditions ( 0) are shown
in Fig. 2. In Fig. 2-a) wormlike micelles are well dened, heads point
out to the aggregate because of the afnity with the solvent. As O
particles increase, the worm shape of aggregates varies from wormlike
(0% of O) to lamellar shape (70% of O particles). In Fig. 2-b) 10% of O
solvent is included and it is encapsulated into micelles; Fig. 2-c) includes
50% of O solvent, which is also encapsulated into the cylindrical

micelles; and Fig. 2-d) contains 70% of O solvent; the shape of the
aggregate is a lamella that encapsulates the W particles.
The corresponding structure factors for the equilibrium microstructures were calculated; results are depicted in Fig. 3. The contribution
of the solvent to the structure factor has been omitted, and only the
coordinates of the surfactant molecules are considered for its
evaluation. In Fig. 3-a) (0% of O solvent) the structure factor presents
two broad peaks oriented at an angle of 45. The axis of symmetry is
shown as a white line, on which the structure factor is projected as a
one-dimension prole. The formation of these peaks is the result of the
solution's anisotropy caused by the micellar aggregates. In Fig. 3-b), the
scattering pattern of 10% of O solvent system is shown; there are two
symmetric regions of peaks with a maximum value of S(kx, ky) = 6.76
in the y-direction. Along the x-direction, there are also two incipient
peaks located in the center of the pattern with a maximum value
of S(kx, ky) = 2.53. Further, in this contour plot, two white lines are
included in both x and y directions, on which the one dimension prole
of the structure factor is shown. The shapes of these peaks are in
qualitative agreement with SANS (Small Angle Neutron Scattering)
experiments [52].
In Fig. 3-c) and -d), the structure factors of 50% and 70% of O solvent
are depicted. A white line was plotted on the scattering pattern in order
to visualize the orientation of the highest peaks. Also, these peaks are an
indicative of the well-dened structures; namely, cylinder and lamella,
such as those shown in Fig. 2-c) and -d), respectively.
3.2. Non-equilibrium molecular dynamics
Fig. 4 shows the rheological behavior of the four systems with a
proportion of (a) 0%, (b) 10%, (c) 50% and (d) 70% of O solvent. It is
possible to nd three regions in each ow curve i) rst Newtonian

E.O. Castrejn-Gonzlez et al. / Journal of Molecular Liquids 198 (2014) 8493

91

Fig. 8. Snapshots for = 0.23 and 50% of O solvent particles for a) = 1 (At the starting of the thinning region), b) = 4 (Shear-thinning region), c) = 20 (At the minimum shear
viscosity) and d) = 100 (Shear-thickening region).

region, ii) shear thinning region and iii) shear thickening region, and
some of the ow curves tend to present a second Newtonian region.
Proposed rheological model (see Eq. (15)) ts well to all the data
regions. Table 2 contains the tting parameters of the proposed model
for all of the systems analyzed here.
Despite the evident differences between the equilibrium structures
shown in Fig. 2, there are no signicant differences in the rheograms
depicted in Fig. 4. The zero shear rate viscosities, 0, are almost the
same, as those listed in Table 2. This behavior is a consequence of two
main considerations: the rst is that the densities of all of the systems
studied are the same. Notice that the mass of each particle is equal to
1.0, with no distinction between the solvent-like particles. The second
consideration is related to the applied force eld; the molecular model
is simple using only repulsive potential and the LennardJones potential
to represent the particle interactions. The aforementioned molecular
model considers a weak intermolecular interaction, so it does not
cause a signicant change in the viscosity values as related to the
molecular structure. On the other hand, the effect of surfactant concentration generates a considerable change in the viscosities values.
For the concentration: = 0.23 and 0% of O-solvent, the effect of the
shear rate on molecular structures is shown in Fig. 5. Snapshots of the
system are depicted for the key shear rates. Fig. 5-a) shows the
well-dened micelles. As the shear rate increases, the micelles align in
the ow direction until lower viscosity is reached. At this point, the
micelles are subject to a disaggregation process where the surfactant
molecules are being dispersed across the volume of simulation
[see Fig. 5-c)]. This break-dispersion mechanism generates the
shear-thickening phenomenon, as reported by Edwards et al. [45].
Complementary structural information is presented in Fig. 6 only for
the highest concentration, = 0.23, and 0% of O solvent, at the same

shear rates as in Fig. 5. At low shear rate ( 1:0) the structure factor
has peaks in the center of the pattern, which corresponds to well
dened wormlike micelle; as the shear rate is increasing, the peaks
move away from the center and new peaks emerge in the gradient
direction (y-axis); which is an indicative that the structure of aggregates
has been deformed. For the lowest apparent viscosity [see Fig. 6-c)]
there are many peaks aligned in the y-axis and small peaks begin to
emerge in the x-direction; these small peaks become higher in Fig. 6-d),
which suggests that molecular dispersion is major.
As illustrations, snapshots for the highest concentration of the
surfactant with different proportions of O solvent are depicted in
Figs. 7, 8 and 9. When a 10% of O particles is added, these particles are
encapsulated into thin cylindrical micelles [see Fig. 2-b)]. At low shear
rates, the cylinders are aligned into the ow direction keeping the
solvent encapsulated. In Fig. 7 we present the snapshots of the system
1:0; 4:0; 10:0 and 60:0 ; corresponding to
at the shear rates of
Newtonian plateau, shear-thinning region, minimum viscosity, and
shear-thickening region, respectively. In the thinning region the cylinders are aligned into the ow direction, and surfactant molecules
begin to separate from the aggregates. The shear-thinning region is
apparently associated to the rupture of the wormlike micelles and also
to the subsequent banded distribution of the surfactant molecules
along to the ow direction [30,53].
The system with 50% of O solvent begins with a cylindrical structure when equilibrium conditions are presented [see Fig. 2-c)].
In this gure, the O solvent is encapsulated into the cylinder with
the hydrophilic heads pointing out to the micelle. The shear thinning
region appears at the (low) shear rate of gamma = 1.0 where the
micelle is well dened and the cylinder is oriented into the ow
direction, as shown in Fig. 8-a). Only in the rst snapshot the O

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E.O. Castrejn-Gonzlez et al. / Journal of Molecular Liquids 198 (2014) 8493

Fig. 9. Snapshots for = 0.23 and 70% of O solvent particles for a) = 1, clear particles correspond to W solvent (included for clarity purposes), b) = 4 (Thinning region), c) = 20
(At the minimum shear viscosity) and d) = 100 (Shear-thickening region).

solvent particles are displayed. However, for the sake of clarity these
particles are eliminated from Fig. 8 b) to d). In the shear thinning
region, at 4:0 the cylinder is still well dened, but the orientation
in the ow direction is more evident [see Fig. 8-a)]. Some surfactant
molecules are even separated from micelles and aligned in the
ow direction; such alignment causes the thinning effect. At the
minimum apparent viscosity, 20, the cylinder is broken and the
surfactant molecules are totally aligned into the ow direction;
however, these surfactant molecules stay at the same position of
the simulation box. At the highest shear rate of 100, the surfactant
molecules disperse across the entire simulation box [see Fig. 8-d)],
causing the shear-thickening behavior [45].
In Fig. 9 the snapshots for 70% O solvent are depicted. In this case,
only the rst snapshot displays the W solvent particles. At the low
shear rate of 1:0, the ow regime is Newtonian and a lamella is
well dened. In this case, the W solvent is encapsulated into the micelle
and the head of the surfactant molecules point inward the micelle
[see Fig. 9-a)]. When a shear rate of 4:0 is imposed, the lamella is
deformed and tends to form a cylinder with the head of surfactant
pointing inwards [see Fig. 9 b)]. At this ow regime, shear thinning is
observed. At the minimum apparent viscosity, 20, the cylinder is
deformed and some of the surfactant molecules are disaggregated
and aligned in the ow direction [see Fig. 9-c)]. At the high shear rates
of 100, the surfactant molecules are completely disaggregated and
dispersed in the entire simulation box [see Fig. 9-d)]; causing again
the shear-thickening phenomenon.
All the molecular structure snapshots were developed in the OVITO
(The Open Visualization Tool) software [54].

4. Conclusions
NEMD simulations were performed to determine the rheological behavior of micelles in solution. The ow curve obtained presents three
regions i) a Newtonian plateau, ii) a shear-thinning region, and iii) a
shear-thickening region; we propose a rheological model which reproduces accurately all the data obtained by molecular dynamics. Despite
the simplicity of the force eld used to simulate surfactants in solution,
the micelle formation is in accordance to the results reported by others
authors. Structure factor is determined to complement the structural information about micelle aggregates; peaks in the scattering pattern
emerge along the gradient direction where shear-thinning is present;
the formation of peaks in the ow direction is observed in the shearthickening region. All of these phenomena are a consequence of ow;
specically, the shear-thickening effect is a consequence of the micelle
breaking and the subsequent dispersion of the surfactant molecules.
Acknowledgments
The nancial support of DGEST (No. 4529.12-P), CONACYT
(Nos. 129962 and 104672) and UATx (No. CACyPI-UATx-2014),
is gratefully acknowledged.
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