13052 J. Phys. Chem.

B 2010, 114, 13052–13058

Brownian Dynamics Study of Gel-Forming Colloidal Particles

P. H. S. Santos,*,† O. H. Campanella,† and M. A. Carignano‡

Department of Agricultural and Biological Engineering, Purdue UniVersity, 225 South UniVersity Street, West
Lafayette, Indiana 47907, United States, and Department of Biomedical Engineering and Chemistry of Life
Processes Institute, Northwestern UniVersity, 2145 Sheridan Road, EVanston, Illinois 60208, United States
ReceiVed: June 21, 2010; ReVised Manuscript ReceiVed: September 9, 2010

Brownian dynamics simulations are used to study the formation process of colloidal gels and the effect of
particle concentration on their rheological properties. To model the interaction between particles, we adopted
an R-shifted 12-6 Lennard-Jones (LJ) potential, which allows independent control of the particle size and
attractive range. For a short-ranged potential, the percolated network characteristic of a gel exhibited a
viscoelastic behavior of weak gels. The storage modulus (G′) increased with the particle concentration increase.
Moreover, the dependency of storage modulus (G′) on the particle concentration followed a power law function,
which is commonly reported in the literature for experimental data. Simulating frequency sweep tests showed
that the system behaved as a liquid-like or solid-like material, depending on the frequency applied. The crossover
frequency, i.e., the frequency at which G′ and G′′ are equal, appears to shift slightly to lower values when the
particle concentration increases, suggesting a more solid-like behavior for systems with higher particle
concentration. During gelation, the storage modulus increases as a stretched exponential and reaches a constant
value at long times.

Introduction order to get a better understanding about irreversible colloid

Gels formed by colloidal particles are soft materials rich in
solvent with distinctive viscoelastic properties.1 Colloidal
suspensions can be induced to aggregate by adding destabilizing
agents.2 If the particle concentration is high enough, a desta-
bilizing colloidal suspension will form a space-filling network
rather than disconnected clusters. The resulting percolated cluster
constitutes the skeleton of the gel. This skeleton has a
characteristic internal dimension around 10 to 100 times the
particle size, leaving large open regions that are occupied by
the low molecular weight solvent. There are many examples of
colloidal gels in many different areas. Yogurt and many dairy
products are colloidal gels where the particles are large proteins
or protein aggregates.2-5 In the pharmaceutical industry, col-
loidal topical formulations formed with liposomes are used as
drug carriers.6 In more recent years, there has been a surge of
interest in nanotechnology and the use of nanocomposite gels
in the design of biocompatible complex materials for biomedical
devices and drug delivery systems.7 Biodegradable and noncy-
totoxic three-dimensional (3-D) gels arise as an emergent
alternative in tissue engineering and in cell culture.8-10 For other
applications, the flow properties of some colloidal gels may also
convey high performance and improved safety for rocket
propellants, combining properties and advantages of solid and
liquid fuels.11,12
The destabilized and aggregated colloidal network may be
either permanent or transient, depending on the attractive forces
between particles in the system.13 Very strong attractions or the
formation of chemical bonds at relatively low volume fractions
may result in irreversible gels by permanent fractal aggregation,
resulting in a large interconnected network.14 Several experi-
ments and computational simulations have been carried out in
* To whom correspondence should be addressed. E-mail: psantos@
purdue.edu.
†
Purdue University.
‡
Northwestern University. E-mail: cari@northwestern.edu.
10.1021/jp105711y  2010 American Chemical Society
Published on Web 09/28/2010
aggregation.15-18 Reversible gelation leads to the formation of
transient gels. In this article we will only consider reversible
gels: gels formed by particles that do not make permanent bonds.
Namely, colloidal gels form under temperature and concentration
conditions that will eventually lead to a phase separation of the
system. Therefore, the gel is a transient state undergoing a very
slow process that tends to evolve toward a heterogeneous system
with a particle-rich phase in contact with a solvent-rich phase.
Under certain conditions, this slow phase separation process
may be completely arrested,1,19 and the system remains trapped
in the gel state. In the cases where the phase separation
continues, the time scale of this process is usually very long
(days to years) compared with the time scale of the application
of the gel. It is known that particle gels exhibit local ordering;
however, they have no long-range correlations.20,21
Computer simulations of transient colloidal gels have been
carried out for systems with short- and long-range attractive
potentials.22-24 In this context, we refer to short- and long-range
interactions as determined by the ratio between the effective
attractive range and the size of the particle. A ratio that is larger
or equal to one characterizes a long-range potential, as is the
case for 12-6 Lennard-Jones. A ratio that is much smaller
than 1 corresponds to a short-range potential, as is the case for
72-36 Lennard-Jones. Lodge and Heyes20,25-29 extensively
studied systems interacting with Lennard-Jones 2n-n poten-
tials. By taking different values for n, the ratio of range to
particle size changes, affecting the gelation properties of the
model. It is clear that the magnitude of the range of the
interparticle attraction relative to their size has a profound effect
on the system phase diagram.30 For example, Lennard-Jones
particles have a well known phase diagram with the approximate
shape of an inverted parabola that displays a gas/liquid
coexistence curve characterized by a approximate critical point
T* ∼ 1.31 and F ∼ 0.316.30 When the attractive range becomes
Brownian Dynamics Study J. Phys. Chem. B, Vol. 114, No. 41, 2010 13053

extremely short, the liquid phase becomes metastable and there
is a gas/solid phase transition for those systems.30-32
Weak gels are thermodynamically unstable systems in which
the active gellant agent forms a fragile and space-filling network.
Spherical particles may form weak gels if the range of the
attraction between the particles is considerable smaller than the
characteristic size of the particles. At sufficiently low temper-
ature, the short-ranged potentials lead to the formation of gels,
while longer range potentials (for example Lennard-Jones
12-6) tend to result in a faster phase separation. However,
depending on the time scale studied, a transient gel structure
can also be observed for long potential range.28 Performing
Brownian dynamics simulations for a short-ranged potential,
we show the formation of transient gels at low packing fractions
for relatively long simulation times. Most of the efforts on
colloidal systems focus on gelation routes of transient gels and
on the development of a general theoretical framework that
covers all concentration ranges, including high packing fractions.
It is still a challenge to link macroscopic properties of materials
with their microstructural properties and conformation. In
practice, macroscopic properties of gels provide important and
useful inputs to the design of new materials, and that is the
reason why most fundamental research on gels describes their
properties in terms of viscoelasticity. In this paper we use a
rheological approach to study short-ranged transient gels and
which relates the friction constant to the radius of the sphere,
a, and the viscosity of the pure solvent, η. Finally, the
Stokes-Einstein relation establishes the connection between the
diffusion process and the thermal energy
k BT kBT
D0 ) ) (4)
γ 6πηa
Considering that our model particles interact by a smooth
continuous interaction potential, there is no clear definition of
the particle radius and the range of attraction between the
particles. We will define an effective diameter following the
Weeks-Chandler-Andersen theory:33,34
σeff ) ∫0∞ [1 - e-U rep(r)/kBT
]dr (5)
where Urep(r) is the repulsive part of the interparticle potential.
Therefore, our time unit is expressed in terms of σeff instead of
the radius of particle a. Then the time unit can be defined as
2
σeff /4D0.
To model the interaction between colloidal particles, we
adopted an R-shifted 12-6 Lennard-Jones potential:

{ [(
the effect of particle concentration on the gel formation and on
∞, r e R0

) ( )]
their mechanical properties using computer simulations. The
main objective is to get a better understanding about relations U(r) ) 4ε σ 12
-
σ 6
, r > R0 (6)
between microstructural and macroscopic (viscoelastic) proper- r - R0 r - R0
ties of colloidal gels.
where r is the distance between the centers of the particles and
Model and Simulation Details R0 is the shifting distance. In all the simulations, a spherical
We performed Brownian Dynamics (BD) simulations in the cutoff was imposed at rc ) R0 + 2.5σ. This interaction potential
overdamped limit. Namely, we numerically integrate the position allows for an independent control of the size of the particles
Langevin equation: through the shifting distance R0 and the range of attraction
through Lennard-Jones parameter σ. Taking ε as the unit of
energy, and σeff as the unit of length, we can rewrite the
dri 1 interaction potential in the reduced form:
) fi(t) + θi(t) (1)
dt γ
U(r)
)

{ [(
where γ is the friction constant, the same for all the particles, ε
fi(t) is the force acting on particle i due to the interaction with ∞, r' e R0/σeff
the other colloidal particles, and θi(t) is a random noise satisfying
〈θi(t)θi(t)〉 ) 2δijδ(t)kBT/γ. Here kB is the Boltzmann constant
and T the absolute temperature. The hydrodynamic interaction
4
1
r' - R0/σeff ) (
12
-
1
r' - R0/σeff )]6
, r' > R0/σeff (7)

among the particles is beyond the scope of this work and is not
considered. It is also convenient to introduce the reduced temperature
Within the Einstein-Smoluchowski theory of Brownian T* ) kBT/ε. All the simulations presented here are with N )
motion, the mean square displacement of a particle is given 2000 particles and constant volume V. In order to prevent
by: particle overlap, a sufficiently small time step was used (8 ×
10-6σ2eff/4D0) and no special provision was implemented to avoid
the region of infinite potential energy. We use σeff as a nominal
〈r2〉 ) 6D0t (2) size (diameter) of the particle and define the volume fraction
by

where D0 is the diffusion coefficient of the particles at infinite Nπ 3

dilution. From here we can define the unit of time, as is usually
done in BD simulations, as a2/D0, where a is the radius of the
particles. This time unit is proportional to the time needed by
an isolated particle to diffuse a distance proportional to its size.
At this point and to complete the computational framework,
we introduce Stokes law:
γ ) 6πηa (3)
φ) σ (8)
V 6 eff
For particles interacting through a potential with R0 ) 9,
σ ) 1, and T* ) 0.2, the nominal diameter or σeff corresponds
to 10.075σ.
The initial configuration for all simulations corresponds to a
random configuration obtained by running a short molecular
dynamics simulation at high temperature. The initial potential
13054 J. Phys. Chem. B, Vol. 114, No. 41, 2010
Figure 1. Potential energy as a function of time for a system interacting
via standard Lennard-Jones 12-6 potential. The insert shows the initial
100 time units in which the particles form a percolated cluster. The
drop in U between t ) 200 and t ) 300 corresponds to the breaking in
the connectivity of the percolated cluster in one of the Cartesian
directions, and the subsequent reorganization of the system’s structure.
energy is zero or a very small negative number for all the cases,
since there is practically no contact between the particles.
Results
We started our work considering the pure Lennard-Jones
system. This is a particular case of an interaction potential with
R0 ) 0. Even though this system is not in our main interest, it
represents a good test case for the simulation methodology due
to the existence of previous works in similar systems. In Figure
1 we show the time evolution of the potential energy of the
system, for a simulation corresponding to a volume fraction of
φ ) 0.13 and a temperature T* ) 0.2, and in Figure 2 we show
a series of snapshots characterizing the whole process. The
potential energy shows a monotonic decreasing behavior as a
function of time. At first the decrease is very sharp as the
particles cluster themselves to form a gel-like structure with
several branches. Figure 2A shows a snapshot of this transient
gel that remains as such up to a time of t ≈ 200 (in reduced
units). Then there is a major reaccommodation of the branches
as they cluster together to form a single bulky structure, still
percolated, but reducing its surface area as shown in Figure 2B
which corresponds to t ) 500. The formation of the central
bulky structure is reflected by a change in the slope of the
potential energy curve between t ) 200 and t ) 300. The system
keeps evolving and the connectivity across the box in one of
the directions is lost, as shown in Figure 2C corresponding to
t ) 1000. The breaking of the space-filling network is an
Figure 2. Snapshots of the standard Lennard-Jones system at (from left to right) t ) 100, t ) 500, t ) 1000, and t ) 10 000. In the first
two snapshots, the system forms a percolated cluster interconnected through all the faces of the simulation box. At t ) 1000 the connectivity
in the vertical direction has been lost, and at t ) 10 000 the connectivity in a second direction is also broken and the cluster adopts a
cylindrical shape.
Santos et al.
Figure 3. Potential energy of a system with 2000 particles, interacting
with the R-shifted potential with R0 ) 9 and σ ) 1. Different colors
correspond to different volume fractions: 0.10 (black), 0.13 (red), 0.16
(green), and 0.20 (blue). For the intermediate volume fraction, we run
two independent simulations starting from a different initial condition
and with different time steps ((8 × 10-6)σeff
2
/4D0 and (8 × 10-7)σeff 2
/
4D0). Longer simulation was performed for the system with volume
fraction 0.13.
indication of the advance of the separation process. Figure 2D
shows the final structure, at t ) 10 000, that has a cylindrical
shape as the connectivity across the box is maintained only in
one of three directions. Figure 2D also reveals the crystalline
order in parts of the system. Lodge and Heyes20,25-29 previously
reported the formation of transient gels using a Lennard-Jones
2n-n potential, volume fractions of 0.10, 0.16, and 0.20, and
T* ) 0.3. They used 864 particles and a total simulation time
of 81 time units. In their conclusion, they discussed the
surprisingly gel-like behavior of the longest range potential
system (n ) 6). Moreover, they commented that there were no
signs of complete phase separation for the long-range system,
which could be due to the time scale of their simulations, since
those systems tend to phase separate more rapidly. We also
observed visually a gel-like structure using Lennard-Jones
potential (n ) 6), volume fraction of 0.13, and T* ) 0.2 at
short simulation times (t ) 100). However, if the simulation
goes on for longer times, the system no longer exhibits a
percolated network characteristic of gel, which shows the
important role that the potential range and time scale play in
transient gels.
We now consider particles interacting through a short-range
potential, as is the case with R0 ) 9, and σ ) 1. In Figure 3 we
show the time evolution of the potential energy for six
trajectories corresponding to four different volume fractions.
All the simulations were done at the same temperature T* )
Brownian Dynamics Study J. Phys. Chem. B, Vol. 114, No. 41, 2010 13055

Figure 4. Snapshots of a system with volume fraction of 0.13 interacting with the R-shifted potential with R0 ) 9 and σ ) 1 at (from left to right)
t ) 100, t ) 500, t ) 1000, and t ) 10 000. The typical network of a gel remains up to 10 000σeff 2
/4D0.

0.2, and two trajectories starting from different initial conditions

and using a different time step ((8 × 10-6)σeff 2
/4D0 and (8 ×
10-7)σeff
2
/4D0) have been obtained for the intermediate volume
fractions. Judging by the potential energy and also visually
inspecting the simulated trajectories, our results show no
important differences between these two time steps. The volume
fraction has some effect on the kinetics of gelation and on the
final potential energy of the system. All four different volume
fractions show qualitatively the same behavior. There is an initial
fast (t < 10) clustering, followed a process of gel formation (10
< t < 100). For t > 100, the gel keeps evolving at a very low
rate, and no kinetically arrested final state is ever reached. Note
that Figure 3 shows the time evolution for one of the simulations
corresponding to a volume fraction of 0.13 up to t ) 10 000,
confirming that the system keeps decreasing its potential energy,
indicating an accommodation of the particles in more energeti-
cally favorable conformations, and may be a result of aging
process.35 Comparing the structures corresponding to t ) 1000
and t ) 10 000, we see a minor global reaccommodation, but
a larger degree of local ordering is achieved at long times. As
shown in Figure 4, the characteristic network of a gel remains
for the longest simulation time (t ) 10 000). The times in which
the snapshots were taken are equivalent to those presented in
Figure 2 for the pure Lennard-Jones particles.
In Figure 5 we present (A) the time evolution of the size of
the largest cluster in the system, and (B) the time evolution of
the average cluster size for the same systems considered in Figure 5. (A) Size of the maximum cluster as a function of time for
Figure 3. A particle is considered to be part of the cluster if the the system characterized by R0 ) 9 and σ ) 1, and different volume
distance to any of the particles already in the cluster is smaller fractions. (B) Average cluster size as a function of the packing fraction.
than a cutoff distance that corresponds to the first minimum in Different colors correspond to different volume fractions: 0.10 (black),
0.13 (red), 0.16 (green), and 0.20 (blue).
the particle-particle radial distribution function. The four
systems display the same behavior: except for short time
fluctuations, there is a monotonic increase in both the average respectively. These peaks correspond to an fcc lattice. The
and the largest cluster sizes. The time scale to reach total reason why only eight first neighbors are found and not twelve,
percolation is longer for the most diluted systems. This result as is the optimum for hexagonal close packing, is that the system
is expected, since the average initial interparticle distance is has a large exposed surface, as can be seen in Figure 4. The
smaller in the more concentrated system favoring the cluster insert of Figure 6 shows a detail of the local crystalline structure
development. However, it is interesting to note that the time to corresponding to φ ) 0.13, showing sections of two crystalline
achieve total percolation for φ ) 0.10 is approximately 2 orders grains in different relative orientations.
of magnitude longer than the corresponding time for φ ) 0.20. From an experimental point of view, gels can be defined as
This strong dependency could be interpreted in terms of the a system with at least two components: (i) a solvent and (ii) a
slow diffusion of the intermediate clusters that need to travel a gellant that forms a macroscopic space-filling structure that
longer distance in the systems with low concentrations in order provides mechanical rigidity.36 In terms of deformation and flow
to aggregate into a single percolated structure. properties, complex materials such as gels do not follow
The overall structure of the systems at t ) 1000 corresponds Newton’s law of viscosity or even Hooke’s law of elasticity.
to a collection of small clusters fused together. The local Unsteady shear material functions are commonly used to
structure of the system is displayed in Figure 6 for the four characterize gel properties and address their applications. Small
studied systems. The number of first and second neighbors is amplitude oscillatory shear (SAOS) strain is applied to the fluid,
8.0 and 11.6, respectively, and the positions of the first and producing a shear stress wave of the same frequency but usually
second peaks in the g(r) are approximately 1.0σeff and 1.4σeff, not in phase. Knowing the resulting shear stress and phase
13056 J. Phys. Chem. B, Vol. 114, No. 41, 2010
Figure 6. Cumulative g(r) for the system characterized by R0 ) 9
and σ ) 1 at different volume fractions: 0.10 (black), 0.13 (red), 0.16
(green), and 0.20 (blue). The insert shows the crystalline structure of
two flocs in different relative orientation. The g(r) and the snapshot
correspond to t ) 1000 σeff2
/4D0.
difference between stress and strain waves, we can calculate
two properties: storage modulus (G′) and loss modulus (G′′).37
The storage modulus (G′) describes the solid-like (elastic)
characteristic of the system whereas the loss modulus (G′′)
describes its liquid-like (viscous) behavior. These properties are
often determined experimentally38-42 to characterize the rheo-
logical properties of gels since most of them are viscoelastic
materials, i.e., they exhibit both viscous and elastic properties.
In practice, they can describe the material in terms of strength
and weakness, which are useful properties in designing materials
and products. In addition, previous simulations also calculated
the rheological properties of colloidal gels for Lennard-Jones
potential and for systems with irreversible bonds.15,18,28,29,43,44
However, it is still a challenge in different areas such as material
and food sciences to optimize the mechanical properties of
systems and to obtain a better understanding of the relation
between microscopy properties and rheology.2
In order to calculate the viscoelastic properties of the
simulated gels, i.e., the storage modulus (G′) and loss modulus
(G′′), we followed an approach similar to the experimental
setup.15 Namely, we performed Brownian dynamics simulation
on systems undergoing a small amplitude oscillatory shear. The
simulation box was deformed by displacing the top wall normal
to the z-axis following an oscillatory pattern with a fixed
frequency ω. A general triclinic simulation box can be described
by a 3 × 3 matrix. A cubic box is a particular case of a triclinic
box, with all the diagonal elements equal to the length of the
box’s edge, and the off diagonal elements equal to zero. The
oscillatory shear strain that we apply to the simulation box
corresponds to set the xy component of the matrix equal to
γxy(t) ) γ0 sin(ωt) (9)
This oscillatory shear was applied for a very short time, as
compared to the time required for the system to have a
significant change in structure. To calculate the rheological
properties of the system, we used the xy-component of the stress
tensor, which follows an oscillatory function with the same
frequency of the applied strain:
σxy(t) ) σ0 sin(ωt + δ) (10)
The amplitude σ0 and the phase shift δ are obtained from a
fit. Figure 7A shows the simulated sinusoidal strain applied to
Santos et al.
Figure 7. Simulated small amplitude oscillatory shear (SAOS) for the
system R0 ) 9, σ ) 1, and φ ) 0.13, taken at t ) 1000σeff 2
/4D0: (A)
Simulated oscillatory strain (black), stress response (red), and phase
delay (δ) at ω ) 100. (B) Stress response fitting for G′ and G′′
calculations (green). Lxy and Pxy are the xy components of stress and
strain tensors.
the gel (t ) 1000), the shear stress response, and the difference
in phase between them. Figure 7B shows the fitting of the shear
stress response, and constants were used to compute the storage
modulus (G′) and loss modulus (G′′):
σ0
G'(ω) ) cos δ (11)
γ0
σ0
G'
(ω) ) sin δ (12)
γ0
For a purely elastic material, the stress response is in phase
with the strain whereas for a purely viscous material the angle
phase between them corresponds to 90°. The phase angle δ for
viscoelastic materials ranges from 0 to 90°.
The first goal in this work was to determine the regime in
which the stress is linearly related to strain, a standard test
performed in experimental rheology to find the range of linear
viscoelasticity of the sample. Strains of different magnitudes
were applied to the gel, and the storage modulus (G′) was
calculated at a constant frequency (ω ) 10 000 4D0/σ2eff). Figure
8 shows the strain dependence of G′ for gels of different packing
fractions. For all particle concentrations, G′ does not vary for a
range of small strains and exhibits significant reduction when a
certain strain is achieved. This range characterizes the gel’s
linear viscoelastic region, and the strain in which this relation-
ship is no longer linear is defined as critical deformation value
(γc). In addition, Figure 8 shows that the higher the particle
Brownian Dynamics Study
Figure 8. Storage modulus (G′) dependency on maximum strain for
the system R0 ) 9, σ ) 1, and different volume fractions: 0.10 (black),
0.13 (red), 0.16 (green), and 0.20 (blue). All calculations were
performed at a frequency of ω ) 10 000. The calculation was performed
at t ) 1000σeff
2
/4D0.
concentration, the higher the storage modulus (G′), for that
particular frequency. Shih et al.45 developed the scaling fractal
theory which considers that the gel structure is formed by
clusters that aggregate with each other. This theory allows the
collection of structural information on the gels from experi-
mental rheological data. From experimental datan they showed
a power law dependency of the storage modulus (G′ ∝ Øn) and
of the critical deformation (γc ∝ Øn) on the particle concentra-
tion. Two different behaviors were found to describe the gels,
and they were defined in terms of strong and weak links. In a
weak-link regime, both G′ and γc increase with increasing
particle concentration. In a strong-link regime, G′ also increases
as concentration increases (higher dependence than in a weak-
link gel); however, γc decreases as concentration increases. In
addition, the interactions between the colloidal flocs (aggregates)
are stronger than the interactions within flocs in the strong-link
systems. In contrast, in a weak-link gel the interaction within
flocs is stronger than that between aggregates.
We also observe a power law dependency of G′ on particle
concentration for our transient gels. The storage modulus (G′)
satisfies a power law function with an index of 1.04. A weak
dependence of storage modulus on the particle concentration is
observed, which means that G′ increases slowly as packing
fractions increases. The critical deformation (γc), which limits
the linear dependency of G′ on strain, showed a weak
dependence on particle concentration for the studied range.
These results suggest that our system behaves as a weak-link
colloidal gel.
The characteristic behavior of a weak gel shows up also when
simulated frequency sweep tests are performed in the linear
region (γ ) 2.5%) for different volume fractions. This test is
commonly used in experimental studies to investigate the
frequency dependence of the storage modulus (G′) and loss
modulus (G′′). From rheological point of view the flow
properties of weak gels depend on the angular frequency (ω)
of the applied stress.36 The storage (G′) and loss (G′′) modulus
are frequency dependent, exhibiting solid-like or liquid-like
properties depending on the frequency applied. Solid-like gels,
i.e., strong gels, exhibit an elastic modulus much larger than
the viscous modulus (G′ . G′′). Figure 9 shows the simulated
frequency sweep tests for our transient gels. For all particle
concentrations, the colloidal gels displayed a typical viscoelastic
behavior of a weak gel. At low frequencies, the loss modulus
(G′′) is the dominant response of the system, which means that
for that frequency range, the system behaves as a liquid-like
J. Phys. Chem. B, Vol. 114, No. 41, 2010 13057
Figure 9. Storage (G′) and loss (G′′) moduli dependency on frequency
for the system R0 ) 9, σ ) 1, and different volume fractions: 0.10
(black), 0.13 (red), 0.16 (green), and 0.20 (blue). All calculations were
performed in the linear viscoelastic region (γ0 ) 2.5%) and at t )
2
1000σeff /4D0. The insert shows G′ and G′′ as a function of volume
fraction at fixed frequency ω ) 1000.
material. As the frequency increases, both of them (G′ and G′′)
increase. When a certain frequency is achieved, the storage
modulus (G′) exhibits higher values than those of the loss
modulus (G′′). The frequency at which G′ and G′′ are the same
is defined as the crossover frequency. At higher frequencies,
the solid-like characteristic of the material is predominant.
The effect of particle concentration on this solid/liquid like
“behavior transition” can also be observed in Figure 9. As the
particle concentration is increased, the crossover frequency
shifted to lower frequency values, suggesting that higher
concentration systems exhibit a more solid-like behavior. For
the range studied, the higher the concentration, the higher the
frequency range in which the material exhibits solid-like
behavior. The variation of the crossover frequency is not large,
but the change in behavior at ω ) 1000 4D0/σeff 2
confirm this
trend. In the insert of Figure 9, we display G′ and G′′ at ω )
1000 4D0/σeff2
as a function of the volume fraction φ, showing
a larger slope for G′ than for G′′. This dependency implies that
the transition to solid-like behavior happens at lower frequencies
for higher particle concentration. All the macro properties
presented so far were calculated for the gel network formed
after a time of 1000σ2eff/4D0. In order to obtain some information
on the rheology of the system during the gel formation,
conformations of the system at different times were used to
determine G′ during the aggregation process. In Figure 10, the
calculated G′ for φ ) 0.10 and φ ) 0.20 packing fractions is
plotted as function of time. This calculation was performed at
a frequency in which the gels exhibited predominantly solid-
like properties (ω ) 10 000). As the aggregation process goes
on, the storage modulus increases, approaching an asymptotic
value. The higher the particle concentration, the higher the
asymptotic value, implying that solid-like behavior is enhanced
by concentration. In addition, the G′ values during gel formation
increase exponentially according to a stretched exponential of
the form G′ ) G∞ exp-(B/t) . Fitting the data to this function the
k
constants G∞ ) 2.28, B ) 7.29, k ) 0.36, and G∞ ) 4.81, B )
2.37, k ) 0.34, are obtained for φ ) 0.10 and φ ) 0.20,
respectively. The stretching factor k is approximately the same
for the two cases, but the time constant B is significant larger
for the lower concentration. A stretched exponential time
dependency has been observed in the other properties of the
gels, such as the relaxation of incoherent scattering function.46
13058 J. Phys. Chem. B, Vol. 114, No. 41, 2010
Figure 10. Storage modulus calculation for the system R0 ) 9, σ )
1, and volume fractions of 0.10 (squares) and 0.20 (circles) during gel
formation. The calculations were performed in the linear viscoelastic
region (γ0 ) 2.5%), at frequency ω ) 10 000 and t ) 1000σeff 2
/4D0.
Conclusions
Brownian dynamics simulations were performed to study the
relationship between microstructural and macroscopic properties
of transient colloidal gels. We initially considered a standard
Lennard-Jones 12-6 system corresponding to a volume
fraction of φ ) 0.13 and a temperature T* ) 0.1. A transient
gel is formed at relatively short times (t ≈ 100), but due to
major reaccommodation of the branches, the system collapses
to form a single bulky structure with some crystalline local order.
To model particles interacting through a short-range potential,
we adopted a R-shifted 12-6 Lennard-Jones model. Since the
potential range plays an important role in the gel formation,24
the advantage of using this interaction potential is the indepen-
dent control of the size of the particles and the range of
attraction. In addition, we observed that for the case corre-
sponding to R0 ) 9 and σ ) 1, a percolated network
characteristic of a gel is formed for packing fractions varying
from 0.10 to 0.20 and it remains for relatively long simulation
2
times (up to 10 000σeff /4D0). Using a rheological approach, we
characterized those systems and determined their viscoelastic
behavior to investigate the effect of particle concentration on
their mechanical properties. Our simulation results using the
R-shifted Lennard-Jones potential show similar trends and
behavior to those observed experimentally for weak gels. First
of all, the regime in which the stress is linearly related to strain
was determined for all the considered concentrations. As particle
concentration increased, the storage modulus (G′) in the linear
viscoelastic region increased. Moreover, it satisfies a power law
function with index of 1.04. The simulated frequency sweep
tests showed that our colloidal gels behave as a weak gel. For
all particle concentrations, the gels displayed a typical vis-
coelastic behavior. As the applied frequency is increased, the
system undergoes a transition from a liquid-like to a solid-like
material. The frequency at which G′ and G′′ are the same, which
is defined as the crossover frequency, shifts slightly to lower
values as the particle concentration increases, suggesting that
higher concentration systems exhibit a more solid-like behavior.
During the gelation process, the storage modulus (G′), which
in practice characterizes the gel strength, increases as a stretched
exponential as the aggregation goes on, reaching a constant value
for very long times.
Acknowledgment. This work was supported by the U.S.
Army Research Office under the Multi-University Research
Initiative (MURI) grant number W911NF-08-1-0171.
Santos et al.
References and Notes
(1) Zaccarelli, E. J. Phys.: Condens. Matter 2007, 19, 323101.
(2) Mezzenga, R.; Schurtenberger, P.; Burbidge, A.; Michel, M. Nat.
Mater. 2005, 4, 729.
(3) Donald, A. M. Soft Matter 2008, 4, 1147.
(4) Aichinger, P. A.; Michel, M.; Servais, C.; Dillmann, M. L.; Rouvet,
M.; D’Amico, N.; Zink, R.; Klostermeyer, H.; Horne, D. S. Colloid Surf.,
B 2003, 31, 243.
(5) Schurtenberger, P.; Stradner, A.; Romer, S.; Urban, C.; Scheffold,
F. Chimia 2001, 55, 155.
(6) Esposito, E.; Drechsler, M.; Mariani, P.; Sivieri, E.; Bozzini, R.;
Montesi, L.; Menegatti, E.; Cortesi, R. Int. J. Cosmet. Sci. 2007, 29, 39.
(7) Schexnailder, P.; Schmidt, G. Colloid Polym. Sci. 2009, 287, 1.
(8) Wang, Q.; Wang, J.; Lu, Q.; Detamore, M. S.; Berkland, C.
Biomaterials 2010, 31, 4980.
(9) Xie, B. J.; Parkhill, R. L.; Warren, W. L.; Smay, J. E. AdV. Funct.
Mater. 2006, 16, 1685.
(10) Pek, Y. S.; Wan, A. C. A.; Shekaran, A.; Zhuo, L.; Ying, J. Y.
Nat. Nanotechnol. 2008, 3, 671.
(11) Natan, B.; Rahimi, S. Combust. Energ. Mater. 2002, 172. DOI:
10.1615/IntJEnergeticMaterialsChemProp.v5.i1-6.200.
(12) Santos, P. H. S.; Arnold, R.; Anderson, W. E.; Carignano, M. A.;
Campanella, O. H. Eng. Lett. 2010, 18, 41.
(13) Dickinson, E. J. Colloid Interface Sci. 2000, 225, 2.
(14) Dietsch, H.; Malik, V.; Reufer, M.; Dagallier, C.; Shalkevich, A.;
Saric, M.; Gibaud, T.; Cardinaux, F.; Scheffold, F.; Stradner, A.; Schurten-
berger, P. Chimia 2008, 62, 805.
(15) Whittle, M.; Dickinson, E. Mol. Phys. 1997, 90, 739.
(16) Lin, M. Y.; Lindsay, H. M.; Weitz, D. A.; Ball, R. C.; Klein, R.;
Meakin, P. Nature 1989, 339, 360.
(17) Del Gado, E.; Fierro, A.; de Arcangelis, L.; Coniglio, A. Europhys.
Lett. 2003, 63, 1.
(18) Wijmans, C. M.; Dickinson, E. J. Chem. Soc., Faraday Trans. 1998,
94, 129.
(19) Foffi, G.; De Michele, C.; Sciortino, F.; Tartaglia, P. J. Chem. Phys.
2005, 122.
(20) Lodge, J. F. M.; Heyes, D. M. J. Chem. Phys. 1998, 109, 7567.
(21) Toledano, J. C. F.; Sciortino, F.; Zaccarelli, E. Soft Matter 2009,
5, 2390.
(22) Bijsterbosch, B. H.; Bos, M. T. A.; Dickinson, E.; vanOpheusden,
J. H. J.; Walstra, P. Faraday Discuss. 1995, 51.
(23) Bos, M. T. A.; vanOpheusden, J. H. J. Phys. ReV. E 1996, 53, 5044.
(24) Lu, P. J.; Zaccarelli, E.; Ciulla, F.; Schofield, A. B.; Sciortino, F.;
Weitz, D. A. Nature 2008, 453, 499.
(25) Lodge, J. F. M.; Heyes, D. M. Mol. Simul. 1996, 18, 155.
(26) Lodge, J. F. M.; Heyes, D. M. Phys. Chem. Liq. 1996, 31, 209.
(27) Lodge, J. F. M.; Heyes, D. M. J. Chem. Soc., Faraday Trans. 1997,
93, 437.
(28) Lodge, J. F. M.; Heyes, D. M. Phys. Chem. Chem. Phys. 1999, 1,
2119.
(29) Lodge, J. F. M.; Heyes, D. M. J. Rheol. 1999, 43, 219.
(30) Vliegenthart, G. A.; Lodge, J. F. M.; Lekkerkerker, H. N. W. Phys.
A (Amsterdam, Neth.) 1999, 263, 378.
(31) Hagen, M. H. J.; Frenkel, D. J. Chem. Phys. 1994, 101, 4093.
(32) Hasegawa, M.; Ohno, K. J. Phys.: Condens. Matter 1997, 9, 3361.
(33) Andersen, H. C.; Weeks, J. D.; Chandler, D. Phys. ReV. A: Gen.
Phys. 1971, 4, 1597.
(34) Barker, J. A.; Henderson, D. ReV. Mod. Phys. 1976, 48, 587.
(35) d’Arjuzon, R. J. M.; Frith, W.; Melrose, J. R. Phys. ReV. E: Stat.
Nonlinear Soft Matter Phys. 2003, 67, 061404.
(36) Terech, P.; Weiss, R. G. Chem. ReV. 1997, 97, 3133.
(37) Understanding rheology; Morrison, F. A., Ed.; Oxford University
Press: New York, 2001.
(38) Kamp, S. W.; Kilfoil, M. L. Soft Matter 2009, 5, 2438.
(39) Tan, L. J.; Liu, S. P.; Pan, D.; Pan, N. Soft Matter 2009, 5, 4297.
(40) van Riemsdijk, L. E.; Sprakel, J. H. B.; van der Goot, A. J.; Hamer,
R. J. Food Biophys. 2010, 5, 41.
(41) Asai, H.; Masuda, A.; Kawaguchi, M. J. Colloid Interface Sci. 2008,
328, 180.
(42) Oppong, F. K.; Coussot, P.; de Bruyn, J. R. Phys. ReV. E: Stat.
Nonlinear Soft Matter Phys. 2008, 78, 021405.
(43) Whittle, M.; Dickinson, E. J. Chem. Soc., Faraday Trans. 1998,
94, 2453.
(44) Whittle, M.; Dickinson, E. J. Chem. Phys. 1997, 107, 10191.
(45) Shih, W. H.; Shih, W. Y.; Kim, S. I.; Liu, J.; Aksay, I. A. Phys.
ReV. A 1990, 42, 4772.
(46) Del Gado, E.; Kob, W. Soft Matter 2010, 6, 1547.
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