Colloids and Surfaces A: Physicochem. Eng.

Aspects 508 (2016) 316–326

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Bulk and interfacial rheology of emulsions stabilized with clay

particles
Joung Sook Hong a,∗,1 , Peter Fischer b
a
Department of Chemical Engineering, Soongsil University, Seoul 156-743, Republic of Korea
b
Institute of Food, Nutrition and Health, ETH Zurich, 8092 Zurich, Switzerland

g r a p h i c a l a b s t r a c t

h i g h l i g h t s

• Interfacial aggregation of natural/modified clays causes high interfacial modulus.

• High interfacial modulus induces significant emulsion stabilization.
• Low interfacial modulus of natural clays does not induce stabilization.
• High modulus of the bulk oil phase with OMt clays causes stabilization.

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

Article history: This contribution aims to investigate the stabilizing effect of clay particles on oil-in-water emulsions
Received 10 April 2016 using bulk and interfacial rheological measurements. Depending on the surface properties of clay parti-
Received in revised form 27 July 2016 cles, the emulsion showed different rheological responses as a result of different stabilization behavior.
Accepted 22 August 2016
Hydrophilic clays (natural montmorillonite (NMt)) stabilized the emulsion via an interfacial layer with
Available online 23 August 2016
distinguished interfacial modulus (G*interface ), while hydrophobic clays (organically modified montmo-
rillonite (OMt)) stabilized the emulsion by increasing the bulk modulus of the oil phase (G*oil ). In
Keywords:
composite systems, when NMt is present together with cationic surfactant or OMt, complex forma-
Interfacial rheology
Clays
tion at the oil-water interface significantly influenced the rheological response and emulsion stability.

∗ Corresponding author.
E-mail addresses: polymer@ssu.ac.kr, jsook.hong@gmail.com (J.S. Hong).
1
Currently address: Department of Chemical Engineering and Materials Science, Michigan State University, East Lansing, Michigan 48824, USA.

http://dx.doi.org/10.1016/j.colsurfa.2016.08.040
0927-7757/© 2016 Elsevier B.V. All rights reserved.
 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326
Aggregation The high interfacial modulus (G*interface ) of the composite interface stabilized the flocculated droplets more
Interfacial location than the repulsive interaction between droplets. As a consequence, the bulk modulus of the emulsion
Emulsion (G*emulsion ) also increases. Finally it could be shown that with increasing interfacial area (oil-to-water
Stabilization ratio), microscopic and macroscopic stabilization of emulsions could be improved. Rheological study
provided structural information of the complex interface and defined the role of clay particles for the
stabilization.
1. Introduction
Emulsions composed of immiscible phases are thermodynami-
cally unstable. They continuously change structure to minimize the
free energy. Against this nature of emulsion, during emulsification
both, dispersed and continuous phase develop structural domains
depending on composition and due to the external energy input.
The competition of breakup and coalescence results in heteroge-
neous size distribution of droplets. After the emulsifying process,
coalescence between droplets continues and the emulsion finally
separates into its individual phases. Coalescence is a thermody-
namically favorable process driven by net reduction of interfacial
energy and results in film drainage and rupture of the continu-
ous phase film between the dispersed droplets [1,2]. Stabilization
against coalescence is one of the most important parameters to
determine product quality of the emulsion. Thus a large number
of publications focused on the design of stable macro- or micro-
emulsions. For stabilization, small molecular weight surfactants,
block-copolymers, proteins, colloidal particles, and combinations
thereof are added to the emulsions [3–14]. All mentioned materials
form an interfacial adsorption layer depending on concentration,
hydrodynamic condition, and physicochemical properties such
as hydrophilic-lipophilic balance and contact angle. As a result
the dispersed droplets are preserved from coalescence by sev-
eral mechanisms such as electrostatic repulsion, interfacial tension
reduction, and Marangoni stress against film drainage [15–19]. The
combination of surfactant and particles expects to give a synergic
stabilization effect to emulsions by a formation of electrostatically
and mechanically strengthened interface. The head or tail of the
ionic surfactants adsorbs on the surface of particles by electrostatic
attraction and renders the surface more hydrophobic or hydrophilic
[3].
In order to characterize the interfacial adsorption layer, sev-
eral mechanical methods have been developed in the past [20–22].
Since this frontier work in interfacial rheology, the interfacial
layer built-up by particles or surfactants is acknowledged to
have independent mechanical properties than the surrounding
bulk phases. Research on the formation of an interfacial layer of
surfactants, amphiphilic molecules, and particles by using dilata-
tional and shear viscosity measurements contributed to further
understanding of their adsorption kinetics and stabilization effect
[11,19,23–26].
Interfacial adsorption of surface-active materials increases
interfacial modulus (G*interface ) depending on concentration as
expected. However, it takes place over a long time to reach a stable
interfacial structure because interfacial structures keep changing
due to the change of several external conditions such as electrolyte,
temperature, and flow. This structural rearrangement is reflected
in the interfacial modulus (G*interface ). With particles, the interfa-
cial modulus is expected to be high enough to induce stability no
matter how fast they build the interfacial layer [2,13,27,28]. Never-
theless particles showed unpredictable interfacial layer formation,
especially with surfactant or salt. For complex systems including
particles, surfactants, or salt, interfacial rheology combined with
diverse rheological measurement techniques was suggested to
317
© 2016 Elsevier B.V. All rights reserved.
relate the diverse mechanical response to the formation of an inter-
facial adsorption layer [10,11,24,25,29]. This in particular, because
complex physical and chemical interaction compete during the
build-up of an interfacial layer, rapid diffusion of surfactants, as well
as addition of salt to the interface or colloidal particles enhances
precipitation of particles [13] or interfacial accumulation [30].
Despite such remarkable efforts to measure interfacial proper-
ties, we are far from knowing how strong an interfacial modulus
(G*interface ) has to be to provide emulsion stability against the coa-
lescence induced by the density difference between the oil and
aqueous phases or by flocculation of droplets [19,31–34]. Addi-
tionally, it is difficult to predict how the bulk properties of the
emulsion are influenced by the interfacial response of the emul-
sion system after processing. Because the stabilization is obtained
as a result of an integrated association of microscopic interfacial
phenomena of particles and build-up of macroscopic inter-droplets
structure, stabilization of the complicated emulsion system cannot
be obtained if either micro- or macrostructural contributions are
neglected. Therefore, for successful application of particles for the
stabilization of the emulsions, it is necessary to figure out the micro-
scopic/macroscopic motion of particles in the emulsion system
under flow conditions and define their role for emulsion stabiliza-
tion. There are still many challenges remaining to understand the
interfacial phenomena of particles existing in nature and define
their stabilization ability.
In this study, the emulsion stabilization effect of clay parti-
cles was studied due to their abundance in nature, high potential
in many applications such as industrial materials, water treat-
ment [35], biomedical usage [36], and industrial needs to improve
processing efficiency in fluid transport [37,38]. Especially, mont-
morillonite, a member of the smectite group of clay minerals
have been studied as a colloidal particle in diverse applications.
For example, variations of montmorillonite were developed by
exchange of an alkaline metal existing in the interlayer with organic
molecules. For the purpose of understanding their behavior at
the interface and their influence on the emulsion stabilization,
two montmorillonite samples of different surface properties were
chosen and added to an emulsion system. Emulsions with clay
particles, particle mixtures and clay-surfactant blends were inves-
tigated based on the relationship between rheological response and
structure of emulsion systems. Emulsion rheology, interfacial rhe-
ology as well as morphology were expected to provide important
information to suggest the stabilization mechanism of clays in the
emulsion system.
2. Materials and methods
2.1. Materials
For oil-in water emulsions, canola oil (CJ CheilJedang Co., Korea)
was used for the oil phase, which mostly consists of unsatu-
rated fatty acid (91.3%). The oil had a density of 0.85 g/cm3 and
a viscosity of 0.06 Pas at 20 ◦ C. For the water phase, purified
(Barnstead RO pure LP system, Thermo Scientific, USA) and deion-
ized (Nanopure II systems, Thermo Scientific, USA) water was
318 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326
used. Clay samples were purchased from Southern Clay Prod-
ucts Inc. (USA). Two different clay samples were used: natural
Na-montmorillonite and organically modified montmorillonite.
Natural Na-montmorillonite (Cloisite® Na+) (NMt) had a density
of 2.6 g/cm3 . When NMt is organically modified with a surfactant
with a long hydrocarbon tail (C16–18 ), the clay surface had more
hydrophobic characteristics. The organically modified montmo-
rillonite (OMt) was a dimethyl hydrogenated-tallow ammonium
modified montmorillonite (Cloisite® 20A), which was prepared by
exchanging ions in NMt with alkyl ammonium cations. Both clay
samples were added to the emulsion as received. In the emulsion
systems, the size of clays was distributed from several hundreds
of nanometers to several micrometers depending on the degree of
exfoliation and aggregation (supplementary Fig. 1).
2.2. Preparation of emulsions
To prepare clay stabilized emulsion, water, clay particles, and oil
were sequentially added to vessel. The amount of oil and water was
fixed to 5 g and the mixing ratio of oil and water was varied over a
wide range from 30/70 wt/wt to 70/30 wt/wt oil-in-water (O/W).
Plus, an additional mass of clay samples (wtclays /wtoil+water ) were
added to oil and water (5 g). For example, to prepare 40/60 wt/wt
O/W emulsions with 3000 ppm clay, oil of 2 g, clay of 15 mg, and
water of 3 g were added to the vessel and emulsified all together.
The emulsification was performed using a vortex mixer (MX-S,
PRONEER Co., Korea) under fixed stirring conditions of 1600 rpm
for 10 min at room temperature. Right after emulsification, the
emulsion was left under vacuum to remove bubbles (700 mmHg,
5 min) and the separated aqueous or oil phase was not removed.
Pure emulsions without clays were prepared in the same way.
In this study, the emulsion stability was mentioned based on
macroscopic/microscopic observations for 30 min after emulsify-
ing (supplementary Fig. 2–6) because rheological measurement
was finished in 30 min after emulsifying. From the preliminary
stabilization test over a wide range of emulsion compositions (sup-
plementary Fig. 2–6), the 40/60 wt/wt O/W emulsion was used as
the model emulsion because it was the most stable sample.
2.3. Optical observations
After the preparation of the emulsions, they were studied for
macroscopic and microscopic changes. For macroscopic observa-
tions, images (2560 × 1712 pixels) of the vessel containing the
emulsion were taken every 5 min to monitor possible phase sep-
aration. To address microscopic changes, small amounts of the
emulsions were transferred onto a glass slide. The space between
the glass slide and cover glass was consistently set at 180 ␮m. Pic-
tures were taken (1280 × 1024 pixels, Olympus BX43, 4×, 10×, and
20 x lens, Japan) to observe the structure of the emulsion.
2.4. Rheological measurements
For rheological measurements of the emulsions, a sample of
constant volume was used following a predefined procedure to
minimize the effect of emulsion aging. After emulsifying, the emul-
sion had a bubble layer on the top. To exclude bubbles, the emulsion
sample was taken from the middle part of the sample. A dynamic
oscillatory sweep tests were performed using a rheometer (AR-G2,
TA instruments, USA) with a parallel plate fixture (60 mm in diam-
eter) to measure the complex viscosity (␩*(Pas)), storage modulus
(G’(Pa)), and loss modulus (G”(Pa)) as a function of strain and fre-
quency. Prior to frequency sweep test, oscillatory strain sweep test
was performed to confirm the linear viscoelastic condition of strain.
The strain was fixed to 5% for frequency sweep test. The interfa-
cial shear rheology was performed using an Anton Paar Physica
MCR 501 rheometer equipped with biconical geometry [25]. Oscil-
latory amplitude sweep experiments (␻ = 1 s−1 ) were performed
as a function of strain (␥) from 0.01 to 10% and dynamic frequency
sweep experiments (␥ = 0.5%) were performed over the angular fre-
quency (␻) from 0.05 to 10 rad/s. The transient evolution of the
interfacial adsorption layer was investigated by an oscillatory time
sweep for 24 h (␥ = 0.1%, ␻ = 1 s−1 ). Temperature was maintained
for all experiments at 20 ◦ C.
3. Results
3.1. Pure clay adsorption layers
The lack of thermodynamic miscibility between oil and water
continuously drives an oil-in-water emulsion into phase separation
if there is no external mixing energy. Such a continuous struc-
tural change makes it difficult to measure precise and reproducible
rheological properties of the emulsions to provide structural infor-
mation even though measurements are carried out consistently
and repetitively. The oil-in-water emulsion system tested in this
study also never showed stability against phase separation over
the whole composition region. For this oil-in-water emulsion sys-
tem, two clay samples with different surface property were added
to investigate the effect of clays for the emulsion stabilization.
According to our previous study, clays showed different interfa-
cial localization depending on their wetting behavior between oil
and water [39] and also they reduced interfacial tension in dif-
ferent way [40]. As shown in Fig. 1, with the addition of clays
(3000 ppm), the emulsions showed different stabilizing behavior
depending on emulsion composition and clay type (more details
in supplementary Fig. 2–6). Clay particles improved the emulsion
stability against phase separation. Especially, as the amount of the
oil phase increases (increased O/W ratio), the emulsions with OMt
were more stable than those stabilized with NMt.
In order to investigate the stabilization effect of clay particles,
the composition of the emulsion was fixed at 40/60 wt/wt O/W.
The concentration of clay varied from 3000 to 20,000 ppm for both
clay samples. The 40/60 wt/wt O/W emulsion showed average drop
size of 80 ␮m with NMt (3000 ppm), while it was 160 ␮m with OMt
(3000 ppm) (supplementary Fig. 6). As time goes by, the emulsion
stabilized with NMt showed separation of the water phase at the
bottom, while the emulsion stabilized with OMt showed an oil layer
at the top of the emulsion. Even with higher concentration of clay,
the emulsions have the same tendency toward phase separation
(supplementary Fig. 3). Prior to analyzing the rheological data, the
stability of the emulsion samples were macroscopically checked
immediately after the rheological test (∼10 min from loading to
measuring) to ensure the reliability of the test (Fig. 2). In the case of
the 40/60 wt/wt O/W emulsion without clays, the emulsion quickly
started separation after emulsifying. During the measurement, it
was completely separated into two phases. As shown in Fig. 2(a),
the water phase stayed in the center and the oil phase spread out-
side. When the emulsion was mixed with clays, the stability of
the emulsions was significantly improved even though the emul-
sions still showed partial phase separation. With NMt (6000 ppm)
(Fig. 2(b)), the emulsion separated only mildly during the measur-
ing period. The emulsion with OMt (6000 ppm) remained stable
during the rheological measurement (Fig. 2(c)). These macroscopic
observations indicated that clay as a colloidal particle stabilized the
emulsion in different ways depending on the surface properties of
the clay.
The different stabilizing behavior of both clay samples was
reflected in the rheological response of the emulsions. The linear
viscoelasticity response of 40/60 wt/wt O/W emulsions was com-
pared depending on the concentration of two clay samples (Fig. 3).
 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326 319

Fig. 1. Comparison of the emulsion stability depending on emulsion composition and clay type. The images were taken at 30 min after emulsifying. The outer diameter of
vial is 28 mm.

Fig. 2. Optical observation of the emulsion samples after rheological measurement: (a) the 40/60 wt/wt O/W emulsion, (b) the 40/60 wt/wt O/W emulsion with NMt 6000 ppm,
and (c) the 40/60 wt/wt O/W emulsion with OMt 6000 ppm. When the rheological measurement test completed, the upper fixture of measuring geometry was lifted to inspect
the emulsion samples left on the bottom fixture. Also the emulsions remained in the vessel were cross-checked.

Fig. 3. Oscillatory frequency sweep test of the 40/60 wt/wt O/W emulsions depending on the concentration of both NMt and OMt: (a) emulsion storage modulus (G’emulsion )
and (b) emulsion loss modulus (G”emulsion ).
320 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326
Fig. 4. Oscillatory frequency sweep test showing storage and loss moduli (G’oil and
G”oil ) of the oil phase depending on the concentration of OMt.
With NMt, the emulsions were not stable regardless of the concen-
tration of NMt as shown in Fig. 1 and Fig. 2 (b) (supplementary Fig.
2). Storage modulus of the emulsions (G’emulsion ) with NMt showed
a plateau behavior in the lower frequency region. When the con-
centration of NMt was increased from 3000 ppm to 6000 ppm, the
emulsion modulus (G*emulsion ) significantly increased. When more
NMt was added, the emulsion modulus (G*emulsion ) decreased. The
rheological behavior was changed from a gel-like behavior (with
6000 ppm) to a pregel-like behavior (with 20,000 ppm). It means
that the emulsion changes its behavior depending on the con-
centration of NMt. Initially, NMt was expected to localize at the
interface by its balanced wetting behavior [39]. If clays kept accu-
mulating in the interface, the modulus of the emulsion (G*emulsion )
had to be increased or stayed constant with an increasing con-
centration of clays because the addition of NMt slightly changed
interfacial tension of the O/W emulsion with the increasing con-
centration of clays [40], which resulted in slight increase in the
interfacial area of the emulsion. However, the emulsion modu-
lus (G*emulsion ) instead decreased with increasing concentration of
NMt. It means that concentrated NMt tends to desorb to the water
phase rather than accumulate in the interface. Therefore, the emul-
sion modulus (G*emulsion ) did not increase with the concentration
of NMt and the emulsion could not remain stable even though the
concentration of NMt was increased.
On the other hand, the emulsion modulus (G*emulsion ) of the
emulsion stabilized with hydrophobic OMt were almost ten times
higher than those of the emulsion with hydrophilic NMt and kept
increasing with the concentration of OMt. The storage modulus
(G’emulsion ) showed a plateau-like behavior over the entire fre-
quency region between 0.1–100 rad/s. With OMt of 3000 ppm, the
emulsion was not stable and showed phase separation of the water
phase at the bottom. With higher concentration of OMt (6000 and
20,000 ppm), the emulsions were stable (Fig. 1, Fig. 2(c), and sup-
plementary Fig. 2). Since hydrophobic OMt had the unbalanced
wetting behavior between the oil and the water phase and higher
chemical attraction with the oil phase [39], OMt would remain
only in the oil phase regardless its concentration. If the amount
of OMt was recalculated based on the oil phase only (i.e. according
to wtclays /wtoil ), the concentration of OMt in the oil phase is quite
significant and enough to increase the modulus of the oil phase
(G*oil ) significantly (Fig. 4). If OMt (3000 ppm) added in 40/60 wt/wt
O/W emulsion was only dispersed in the oil phase, the concen-
tration increases to 7500 ppm (wtclays /wtoil ) for the oil phase. The
Fig. 5. Oscillatory time sweep test of interfacial storage and loss modulus (G’interface
and G”interface ) of the oil-water interface with adsorbed NMt and OMt clay particles.
oil phase dispersed with OMt increased its modulus (G*oil ) signif-
icantly because OMt dispersed well due to the chemical affinity
between OMt and the oil. The oscillatory frequency sweep test of
the oil phase shows the development of a plateau in the storage
modulus (G*oil ) for low frequencies with increasing amounts of OMt
as shown for 3000 and 6000 ppm in Fig. 4.
A significant increase in the modulus of the oil phase (G*oil )
also increases in the modulus of the emulsion (G*emulsion ), might
delay coalescence and, thus, results in a stable emulsions. This sta-
bilization behavior could be observed only when the composition of
the oil phase was higher than 40%. Bulk rheology of the emulsions
showed that both clay samples with different surface properties
have different stabilizing potential depending on the concentra-
tion of the clay. To specify their interfacial behavior, interfacial
shear rheology of the oil-water interface with both clay samples
was performed. The oscillatory time sweep test of the interface
was carried out to observe long-term interfacial behavior (Fig. 5).
The interface with NMt showed an increasing storage interfacial
storage modulus (G’interface ) due to the continuous sedimentation
of dispersed clay particles to the interface. However, the interfa-
cial moduli (G’interface, and G”interface ) were very low ( « 0.01 Pa m).
Adsorption and interfacial structure of the NMt layer was easily dis-
rupted by shear force and gravity. The stabilization effect of NMt
also could not be improved by increased concentration of NMt. The
oil-water interface with OMt did not respond to the interfacial rhe-
ology tests except displaying a minor loss moduli (G”interface ) [39].
This means that OMt is most probably not located at the interface
as depicted in the inlay graphs of Fig. 5. Related to this, interfacial
tension measurement supports the interfacial rheological results
obtained for both clay samples [40]. The interfacial tension (␴)
of oil droplet was hardly changed by the addition of OMt even
at increased OMt concentration (for pure oil drop, ␴ is 31 mN/m,
oil droplet with OMt 3000 ppm has 27.2 mN/m, and for that with
OMt 5000 ppm, it slightly decreased to 26 mN/m). On the other
hand, for the oil droplet stabilized with NMt, the interfacial tension
decreases with increasing concentration of NMt (supplementary
Table 1). According to the previous study [41], OMt accumulated
only above the interface due to high chemical interaction and never
desorbed to the water phase. Based on both bulk and interfacial
rheology measurements, as well as optical observations, the stabi-
lization behavior of clays was ensured depending on their surface
properties. The stabilization behavior of OMt rather depended on
the concentration dependent flow properties of the bulk oil phase
(clay dispersed in the oil phase) than on their interfacial rheologi-
cal properties. Meanwhile, NMt particles stabilized the emulsion by
 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326 321

Fig. 6. Oscillatory time sweep test showing interfacial storage and loss modulus (G’interface and G”interface ) of the oil-water interface with the clay mixture (NMt/OMt
3000 ppm/3000 ppm). Pictures of the interface with NMt/OMt (right top) and NMt (right bottom) were taken at 3000 s after the build-up of the interface.

Fig. 7. Oscillatory frequency sweep test showing (a) storage and (b) loss modulus (G’emulsion and G”emulsion ) of emulsions with the clay mixture (NMt/OMt 3000 ppm/3000 ppm)
depending on the composition of emulsion.

the interfacial localization even though only a limited concentra-
tion was located at the interface and the interfacial structure was
not strong.
3.2. Mixtures of NMt and OMt clays
As shown in the previous section, both clay samples did not
build up a strong interfacial layer to stabilize the emulsion. In order
to generate an interfacial layer for stabilization, a mixture of both
clay samples showing different stabilizing effect was tested. The
combination of both clay samples was fixed to 3000 ppm/3000 ppm
(NMt/OMt) and they were added to the emulsion. Interfacial modu-
lus (G*interface ) of the oil-water interface with the clay mixture was
measured as a function of time (Fig. 6).
Different from the interface with pure NMt, the interfacial
storage modulus (G’interface ) rapidly increased and exceeded the
interfacial loss modulus (G”interface ). It means that the mixture of
clays rapidly adsorbs at interfacial region and formed an interfacial
layer (see picture in the upper right of Fig. 6). They continuously
developed an associative structure without desorption [41]. Asso-
ciative interaction of heterogeneous mixture of clay samples led
to a network with increasing modulus as a function of time. The
density of networking between clays might increase as clays occu-
pied the interface more. It made the complex interface sustainable
against external hydrodynamic stress, which resulted in strong sta-
bilization of the emulsion. It means that the interface with high
interfacial modulus (G*interface ) is strong enough to resist against
deformation of the contacting phases or to depress the coalescence
induced by net reduction of interfacial energy.
Bulk rheology of the emulsions stabilized with clay mixture was
measured depending on the oil-in-water ratio from 30/70 wt/wt
O/W to 70/30 wt/wt O/W (Fig. 7). For ratios up to 50/50 wt/wt O/W,
the storage modulus (G’emulsion ) showed a plateau behavior over
the entire frequency region. The storage modulus (G’emulsion ) of
the 40/60 wt/wt O/W emulsion with the clay mixture increased as
high as the emulsion with OMt (∼100 Pa) (see also Fig. 3(a)). When
322 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326
Fig. 8. Oscillatory frequency sweep test depicting the (a) storage and (b) loss modulus (G’emulsion and G”emulsion ) of the 40/60 wt/wt O/W emulsions with the clay mixture
(NMt/OMt) depending on the composition of two clay samples.
the ratio increased further to 70/30 wt/wt O/W, the modulus of the
emulsions (G*emulsion ) rapidly decreased below those values of the
30/70 wt/wt O/W emulsion even though the composition of the
viscous oil phase was increased. It means that as the interfacial
area decreases the emulsion separates regardless of the interfacial
modulus (G*interface ). Except for the 40/60 wt/wt O/W emulsion, the
emulsions exhibited the phase separation of the water phase at the
bottom or the oil phase at the top (refer to the vial image in Fig. 7
and supplementary Fig. 4). In other words, the complex interface
only of the clay mixture (NMt/OMt 3000 ppm/3000 ppm) provides
strong macroscopic/microscopic stabilization of the emulsion by
the increased mechanical interfacial property. However, due to the
lack of electrostatic repulsion, it was shown only at the compo-
sition of 40/60 wt/wt O/W emulsion (∼45/55 (v/v) O/W) with the
high interfacial area, otherwise the emulsions were not preserved
from phase separation. The modulus of emulsions (G*emulsion ) sta-
bilized by the complex interface would change only depending on
the interfacial modulus (G*interface ), which also showed the max-
imum value when the droplets coherently flocculated with the
complex interface. If the interfacial layer was formed by the asso-
ciation between clays, the interfacial modulus (G*interface ) would
change according to the composition of the clay mixture. The
40/60 wt/wt O/W emulsions with different combinations of NMt
and OMt was tested (Fig. 8) (the total concentration of clays was
fixed at 6000 ppm).
When both clay samples were added equivalently (1/1
NMt/OMt) or when the concentration of OMt was higher than that
of NMt (1/3 NMt/OMt), the emulsion modulus (G*emulsion ) was high
enough to expect significant stabilization [42]. When the concen-
tration of OMt was lower than that of NMt (3/1 NMt/OMt), the
emulsion modulus (G*emulsion ) was significantly decreased and the
emulsion showed phase separation. In this case, the interaction
between two clay samples was not strong enough to retain NMt
at the interface and then NMt might be desorbed to the phase hav-
ing strong chemical affinity with NMt. It means that the complex
interface is sustained only at the limited combination between NMt
and OMt for the emulsion stabilization.
3.3. Influence of surfactant on emulsion stability
In previous work we have shown that the interfacial localization
of clay particles can be influenced by the presence of surfactant and
thus forming a surfactant-clay compound at the interface [30]. To
investigate the stabilization behavior of clay with surfactant, both
clay samples were tested with CTAB (Cetyltrimethylammonium
bromide, CH3 (CH2 )15 N(CH3 )3 Br4 , CAS no.57-09-0, Sigma-Aldrich)
and SDS (Sodium dodecyl sulfate, C12 H25 NaO4 S, CAS no.151-21-3,
Sigma-Aldrich). The frequency sweep experiments of the emul-
sions with clay and surfactant were compared in Fig. 9.
With the addition of CTAB (3000 ppm) or NMt (10,000 ppm),
the emulsion modulus (G*emulsion ) was lower than 10 Pa and the
emulsions were not stable (see Section 3.1). If they were added
together at the same time, the emulsion modulus (G*emulsion ) had
profoundly increased and the emulsion was significantly stable.
Due to cationic exchange capability of NMt (∼78 meq/100 g dry
clay), CTAB enhanced the association of NMt located at the interface
to build up a strong interfacial layer [30], which was sufficient to
stabilize the emulsion against coalescence (Fig. 9(d)). On the other
hand, if the emulsion was added with OMt and CTAB, the modulus of
the emulsion decreased and the emulsion was not stable (Fig. 9(f)).
Different from the emulsion stabilized with pure OMt (Fig. 3), the
location of OMt in the emulsion is changed by the presence of CTAB
as the surfactant which manipulates the wetting behavior of OMt
between oil and water [30,39]. Coherent location of OMt in the oil
phase to induce the emulsion stabilization could not expect any
more and, as a consequence, the emulsion was no longer stable.
When anionic SDS was tested with both clays, the emulsions never
stabilized. NMt has no interaction with anionic SDS and also the
rapid adsorption of the SDS to the interface changed the localization
of clay [30]. To achieve a synergistic stabilization effect between
clay and surfactant, it is necessary to investigate the surfactant-
colloidal clay particles complexation as well as the difference in
adsorption kinetics between them. The strong and rapid interfacial
adsorption of surfactant enhances desorption of clays [30], which
may result in the phase separation of the emulsion. According to
the rheological properties of the emulsion, stabilization depends
on the concentration of clay, their combination, and the presence of
surfactants. Two effects were observed as either clay stabilized the
emulsion by interfacial layer formation (increase of G*interface ) or by
an increase in the modulus of the oil phase (G*oil ). If the clays had a
strong chemical affinity with the oil phase, they did not localize at
the interface but the emulsion modulus (G*emulsion ) increased with
increasing concentrations of clays especially when the phase con-
taining OMt is the major phase. If clay was localized at the interface,
the emulsion modulus of the emulsion (G*emulsion ) was increased by
the high interfacial modulus (G*interface ) of the interface. It showed
the peak at the optimal concentration of clays since the complex
interface was generated by the association between natural clay,
organically modified clay, or surfactants. As the interfacial area of
 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326
Fig. 9. (a) Storage modulus (G’emulsion ) and (b) loss modulus (G”emulsion ) as a function of frequency for 40/60 wt/wt O/W emulsion stabilized with clay and surfactant (CTAB
and SDS). Optical inspection of the emulsions after the rheological tests: (c) emulsion with NMt (10,000 ppm), (d) with NMt (10,000 ppm)/CTAB (3000 ppm), (e) with OMt
(10,000 ppm), and (f) with OMt (10,000 ppm)/CTAB (3000 ppm).
Fig. 10. Comparison of storage and loss modulus (G’emulsion , G”emulsion ) of the emul-
sion (40/60 wt/wt O/W) as a function of clay concentration. Storage modulus of the
oil-water interface with clays (G’interface ) is compared in the table.
the complex interface increased, it induced a pronounced stabiliza-
tion effect to the emulsion.
4. Discussion
Rheological response of emulsions (G*emulsion ) under deforma-
tion (D) is determined by contribution of the interface (G*interface
323
and Dinterface are interfacial modulus and interfacial deformation)
as well as each phase (G*water and G*oil for the water (␾water ) and
the oil phase (␾oil ) respectively, here ␾ is the faction of each phase)
[1]:
∗ ∗
 ∗

␶emulsion = Gemulsion D = Goil oil + Gwater water D + ␶interface (1)
Since both bulk phases (oil and water) of the emulsion have
negligible modulus, the modulus of emulsions is determined by
the contribution of interfacial stress (␶interface = G*interface Dinterface )
(␶emulsion ∼ ␶interface ). If the emulsion is not compatibilized, the
interfacial stress might be determined by interfacial energy and
interfacial area (␶interface ∼ interfacial tension (␴) × A/V, where A
and V are interfacial area and volume) [1,28,43]. The emulsion
modulus (G*emulsion ) therefore increases with the increasing com-
position of the dispersed phase because of the increase in interfacial
area. Meanwhile, if particles or macromolecules accumulate at the
interface, the interface has independent interfacial stress regardless
of the contacting phases because it has its interfacial flow proper-
ties (surface dilatational viscosity (␬), surface shear viscosity (␩))
by particle motion, interaction, density as follows [22,44]:
I
  D
 
int = I (2) + f Dint + f Dint (2)
I , and DD are interfacial tension, isotropic sur-
where ␴, I(2) , Dint int
face tensor of second order, isotropic and deviatory parts of the
rate of strain tensor, respectively. Because the term f(Dint ) is a
function of surface tensor and rate of strain tensor, the emulsion
modulus (G*emulsion ) will be significantly influenced by interfacial
flow properties of its stabilizing adsorption layer. Even if particles
added to the emulsion, they do not necessarily form an interfa-
cial adsorption layer but also disperse only in the oil phase. Thus
particles significantly increase the rheological property of the oil
phase and influence the determination of the emulsion morphology
due to change in viscosity ratio, which might change the emulsion
324 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326
Fig. 11. Optical microscope image of (a)(b) the 40/60 wt/wt O/W emulsions and (c)(d) the 60/40 wt/wt O/W emulsions with clay (6000 ppm): (a)(c) (1/1)NMt/OMt and (b)(d)
OMt.
modulus (G*emulsion ) in addition to interfacial stress. Depending
on whether the particles locate at the interface, the rheological
response of the emulsion has totally a different tendency toward
the composition of emulsion, the concentration of particles, or
interaction between interfacial localized particles.
According to this study, the O/W emulsions showed different
rheological response depending on clay samples. The emulsion
modulus (G*emulsion ) of the 40/60 wt/wt O/W emulsions is com-
pared in Fig. 10 as a function of clay concentration and clay types,
while the morphology of the emulsions is depicted in Fig. 11.
Because the composition of the emulsion was fixed to 40/60 wt/wt
O/W, the interfacial area did not change significantly with the addi-
tion of clay. For OMt, the emulsion modulus (G*emulsion ) steadily
increased with increasing concentration of clays, while the emul-
sion with NMt or NMt/OMt shows a peak in emulsion modulus
(G*emulsion ) at 6000 ppm. The difference in the emulsion modulus
(G*emulsion ) between OMt and NMt or NMt/OMt is mainly caused
by the location of the clays. OMt disperses well in the oil phase
and it increases the modulus of the oil phase (G*oil ) with increasing
concentration of clay (Figs. 4 and 5). NMt or NMt/OMt is located
at the interface and shown distinct differences in interfacial stor-
age modulus as summarized in the table in Fig. 10. Emulsions with
NMt or NMt/OMt are therefore easily manipulated by the concen-
tration of particles. The comparison of storage modulus (G’emulsion )
and loss modulus (G”emulsion ) of the emulsions shown in Fig. 10
reveals that the emulsion with OMt or NMt has slightly lower stor-
age modulus than loss modulus. It means that their structure is
dissipative under the deformation and the interaction between par-
ticles is not strong enough to resist deformation. The emulsion with
NMt/OMt has a higher storage modulus than loss modulus resulting
in a strong associative network structure, which does not dissi-
pate under deformation. With OMt, the emulsion shows typical
spherical structure (Fig. 11(b), (d)) and the emulsion with NMt/OMt
shows non-spherical structure due to rigid association of interfacial
localized clays (Fig. 11(a), (c)).
This rheological study suggests two different stabilization
mechanisms by the added clay samples. For organically modified
clay (OMt), distinguished rheological properties of the oil phase
containing clay effectively delay the diffusion of domains and pre-
vent coalescence when the oil phase is the major phase. On the
 J.S. Hong, P. Fischer / Colloids and Surfaces A: Physicochem. Eng. Aspects 508 (2016) 316–326
other hand, natural clays (NMt) stabilize the emulsion due to the
formation of droplets flocculation induced by interfacial localiza-
tion [39]. It is difficult to expect stabilization behavior until clays
coherently occupy the interface. When droplets approach, the com-
plex interface prevents coalescence and the droplets flocculate to
the cream phase due to their weak colloidal properties. However,
the interfacial layer by NMt is not strong enough to resist mechan-
ical stress during emulsification. The addition of both, OMt and
cationic surfactants enhances the interfacial localization, adsorp-
tion, and aggregation of NMt, which enhances the mechanical
strength of the interface. This suggests that natural clays can give
a significant stabilization behavior if they co-exist with substances
such as surfactants to induce strong interfacial interaction between
clays [30,41,42,45–48].
To further understand the stabilization nature of clays, studies
on the organic compound-clay complex interface have to be carried
out with different clay minerals as well as surfactants. Substantially,
in order to obtain a stable emulsion, the emulsion system needs to
maintain the structure for the stabilization homogeneously even
though each phase plays a critical role in building-up the structure
for stabilization. Accordingly the bulk properties of the emulsion
(G*emulsion ) are significantly useful to know the macroscopic struc-
tural information. The interfacial modulus (G*interface ) also provides
important information about the build-up of the interface, kinet-
ics and interaction between particles. Then, rheology study of the
emulsions provides macroscopic and microscopic structural infor-
mation, such as interfacial localization, the role of particles to
flocculation, which would be difficult to obtain only from morphol-
ogy observations.
5. Conclusions
The stabilizing behavior of clay particles in emulsions was stud-
ied based on the rheological response of the emulsions depending
on the localization, concentration, combination of clays, and pres-
ence of surfactants. Clays stabilized the emulsion by interfacial
layer formation (G*interface ) or an increase of the bulk oil modu-
lus (G*oil ). If clay was simply adsorbed at the interface without
strong interaction, the interfacial adsorption layer (G*interface ) was
not strong enough to prevent coalescence, which also resulted in
low bulk moduli of the emulsion. Formation of a complex inter-
face was obtained by strong association between two clays with
different surface properties or between clay and CTAB, which sig-
nificantly increased the interfacial modulus (G*interface ). Thus, the
adsorption layer at the interface was strong enough to provide a
barrier against droplet coalescence. Further the emulsion modu-
lus (G*emulsion ) increased significantly and stabilized the emulsion.
Both mechanisms give a significant macroscopic/microscopic sta-
bilization to the emulsion as the interfacial area increased which
resulted in high storage modulus of the emulsion (∼100 Pa for
G’ of the 40/60 wt/wt O/W emulsion with 6000 ppm OMt or
3000 ppm/3000 ppm NMt/OMt).
Acknowledgement
This study was supported by Mid-career Researcher Program
through NRF grant funded by the Korea government (MEST) (No.
20110016890).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.colsurfa.2016.08.
040.
325
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