Colloids and Surfaces A: Physicochem. Eng.

Aspects 457 (2014) 49–57

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

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

Influence of a mixed particle/surfactant emulsifier system on

water-in-oil emulsion stability
Alla Nesterenko, Audrey Drelich ∗ , Huiling Lu, Danièle Clausse, Isabelle Pezron
EA 4297 Transformations Intégrées de la Matière Renouvelable UTC/ESCOM, Université de Technologie de Compiègne, rue Personne de Roberval, 60200
Compiègne Cedex, France

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

• Synergic stabilization of W/O

emulsion was allowed using
particles/surfactant system.
• Emulsion stability was reduced with
the increase of surfactant concentra-
tion.
• Maximal emulsion stability was
obtained with a small amount of
surfactant.
• Emulsion was stabilized by particu-
lar 3D network with fine drops and
particles.

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

Article history: Water-in-oil (W/O) emulsions consisting of water and paraffin oil were prepared and stabilized by using
Received 31 March 2014 a dual emulsifier system including hydrophobic silica particles and non-ionic surfactant. The surfac-
Received in revised form 16 May 2014 tant/particles synergistic interaction and more specifically the effect of surfactant concentration (from
Accepted 19 May 2014
0 to 1.8%, w/w) at fixed amount of particles (1.8%, w/w) on the emulsions properties were investigated.
Available online 27 May 2014
Interfacial tension, emulsion morphology, water droplet size distribution, stability with time, rheologi-
cal stress–strain and oscillatory properties were determined to better understand the interaction and
Keywords:
mechanism of emulsion stabilization by solid particles in presence of surfactant. The results showed the
Water-in-oil emulsion
Pickering emulsion
existence of strong interaction between surfactant molecules and silica particles. The critical micellar
Mixed particle/surfactant emulsifier concentration for the mixed-emulsifier system was significantly higher than that of surfactant alone. In
Silica particles presence of a low amount of surfactant (0.1%, w/w), the emulsion was characterized by maximal stability
Rheology (up to 21 days without any phase separation). This dependence was confirmed by rheological measure-
Emulsion stability ments which revealed a highest storage modulus (G ) value for this emulsion. Optical microscopy revealed
the formation of closely packed aggregates of small droplets forming bridges between neighboring large
drops, at low surfactant concentration. The possible explanation for this phenomenon could be the floc-
culation of small emulsion droplets in the presence of low amount of surfactant. The formation of flocs
caused the thickening of the continuous oil phase, the increase in emulsion rigidity and consequently
enhanced emulsion stability.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction

Water-in-oil (W/O) emulsions have different applications in the

food, pharmaceutical, petrochemical and cosmetic industries [1,2].
∗ Corresponding author. Tel.: +33 03 44 23 44 23. In practice, emulsion is a thermodynamically metastable system,
E-mail address: audrey.drelich@utc.fr (A. Drelich). and therefore the main challenge for W/O production is to control

http://dx.doi.org/10.1016/j.colsurfa.2014.05.044
0927-7757/© 2014 Elsevier B.V. All rights reserved.
50 A. Nesterenko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 49–57
the system stability as well as provide its protection against desta-
bilization. The separation of the oil and water phases of emulsion
can be observed during storage and/or under effect of temperature
and addition of electrolyte compound [3,4]. The common desta-
bilization mechanisms in emulsion are flocculation, coalescence,
sedimentation and Ostwald ripening [5–7]. Fluid W/O emulsions
generally present lower stability, compared to oil-in-water (O/W)
emulsions and can easily coalesce, flocculate or sediment [2]. More-
over, contrary to O/W emulsions stabilized by both steric and
electrostatic repulsion, only steric forces are expected to stabilize
W/O due to the low conductivity of the continuous phase. For the
last decade, the better understanding of emulsion stabilization and
destabilization mechanism has become an increasingly interesting
area for research.
Surfactant molecules with low hydrophile–lipophile balance
(HLB), such as polyglycerol polyricinoleate, sorbitan ester surfac-
tants (Tween and Span series) and soy lecithin, are well known
as emulsifiers used to prepare W/O emulsions [8–11]. More
recently, considerable progress has been made in the area of
solid-stabilized emulsions (called Pickering emulsions) using sil-
ica, oxides, clay, alumina, carbon, fat crystals and polymer lattices
[12–15]. Furthermore, the use of mixture of surfactant and particles
for emulsion stabilization has attracted research and commercial
attention for the reason of interactions occurring in such systems.
However, fewer studies are devoted to the influence of mixed
particle/surfactant emulsifier system in W/O emulsion, and the
mechanism of emulsion stabilization remains poorly understood.
Addition of surfactant molecules to particle system or vice versa
influence their efficiency as emulsifiers [12]. Consequently, the
properties of emulsions obtained are dependent on the syner-
gic interactions between particles and surfactant at the emulsion
droplet surface and in the bulk [16,17]. The surfactant has multiple
functions in the stabilization of O/W emulsion in the presence of
particles: to decrease the interfacial tension favoring droplet for-
mation, to adsorb on the particles surface affecting their wettability
and, in some cases, to allow the flocculation of solid particles [18].
Binks et al. [12] showed that in the presence of constant amount
of silica particles, the stability of O/W emulsion was improved
at low surfactant (alkylpoly(oxyethylene)) concentrations. In such
system the synergy between particles and surfactant resulted in
the emulsion viscosity increase and significant enhancement in the
emulsion quality. The fine emulsions of excellent long-term stabil-
ity was obtained in the case of surfactant adsorption on particles
which was followed by particle agglomeration and adsorption of
such agglomerates at the oil/water interface. With the increase of
surfactant concentration the displacement of particles by surfac-
tant from the oil/water interface can occur [19] which resulted in
the particle network breakdown and emulsion destabilization. The
findings from other studies [20,21] demonstrates that the increase
in surfactant concentration at a fixed amount of solid particles led
to higher cream layer volume which was attributed to the reduction
in O/W emulsion droplet size. This discrepancy between published
results was probably due to the experimental conditions differ-
ences, but essentially to different variety of surfactant molecules
and not the same mechanism of stabilization.
The synergic stabilization mechanism of high internal phase
W/O emulsion was proposed by Zou et al. [22]. Here the authors
demonstrated that neither surfactant nor particles was suitable
to emulsion stabilization. However, the dual emulsifier sys-
tem allowed satisfactory result for emulsion preparation. In the
obtained W/O emulsion, big emulsion droplets were preferentially
stabilized by particles, while small ones were preferentially sta-
bilized by surfactant molecules. Thus, the increase in particles
concentration resulted in higher amount of big emulsion droplets,
and the increase in surfactant concentration favored the forma-
tion of fine emulsion droplets. Therefore, the wide droplet size
distribution played a key role for the synergic stabilization of W/O
emulsion with mixed emulsifier system.
Our previous work [5] dealt with W/O emulsion stabilized
by non-ionic emulsifier or with hydrophobic silica particles. The
results obtained evidenced the difference in the stabilization
mechanisms between the two systems. Solid particles efficiently
stabilized the emulsion droplets by forming a network in the
oil phase acting as a steric barrier to coalescence in emulsion.
After addition of surfactant in particle stabilized W/O emulsion,
a progressive destabilization was observed and explained by the
destruction of the particle network by surfactant molecules.
The challenge of present study is to better understand the
specific interactions between particles and surfactant and their
effect on emulsion stabilization or destabilization processes. To this
purpose, W/O emulsions were prepared and stabilized by silica
particles solely or mixed with surfactant. The effect of surfactant
concentration at a fixed amount of particles on emulsion proper-
ties was investigated. The evolution of emulsion morphology and
droplet size distribution as function of added emulsifier was fol-
lowed by optical microscopy and laser diffraction. The physical
stability of emulsion with time was assessed by visual separation
phases observations. Moreover, the rheological measurements pro-
vided the information about viscoelastic and structural properties
of emulsions. The results reported herein contributed to better
comprehension of W/O stabilization mechanism using dual par-
ticle/surfactant emulsifier system.
2. Materials and methods
2.1. Materials
The paraffin oil characterized by a low viscosity (32 mPa s,
density of 0.85 g/cm3 ) was purchased from Carl Roth GmbH
(Karlsruhe, Germany). The aqueous phase was high-purity water
with a resistivity of 18.2 M cm produced by a Lab purification
chain (Aquadem/Veolia, Wissous, France). Amorphous fumed sil-
ica particles (Aerosil® R711) provided by Evonik Industries AG
(Rheinfelden, Germany) were used in this study. Fusion of pri-
mary spheres (diameter of 12 nm) into structured aggregates
(100–200 nm) during combustion process, led to the formation of
branched silica network representing the morphology of particles
[5,23]. The partial substitution of silanol groups by methacrylsilane
moieties resulted in the hydrophobic character of Aerosil® R711
particles. The non-ionic lipophilic emulsifier (HLB of 4.3), sorbi-
tan monooelate or Span® 80 was purchased from Sigma–Aldrich
(Buchs, Switzerland).
2.2. Emulsion preparation
The external oil phase was prepared by dispersing different
amounts of Span® 80 (0.1–1.8%, w/w) in paraffin oil and the disper-
sion was stirred for 15 min at room temperature (20 ± 3 ◦ C) under
magnetic stirring at 800 rpm. The fixed amount of hydrophobic sil-
ica particles (1.8%, w/w) was added to paraffin oil (with or without
Span® 80). The obtained mixture of emulsifiers in paraffin oil was
homogenized at 24,000 rpm for 3 min using Ultra-Turrax T25 high
speed homogenizer equipped with dispersing element S25N-10G
(Jankel & Kuntel, Staufen, Germany) in order to allow maximum
particle dispersion. The W/O emulsion of 10 g was prepared by
adding drop by drop a known volume of water to the obtained
continuous oil phase. The ingredients were then mixed with the
same homogenizer operating at 24,000 rpm for 5 min. The volume
fraction of water in all emulsions obtained was 30%. Experiments
were carried out in triplicate.
 A. Nesterenko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 49–57
2.3. Interfacial tension measurements
Water/oil interfacial tension measurements were carried out by
use of a K100 Krüss tensiometer (Hamburg, Germany) equipped
with a Du Noüy ring geometry. Water/oil interfacial tensions were
determined at different concentrations of Span® 80 from 0.001 to
2% (w/w). To evaluate the silica particles effect on surfactant inter-
facial properties, dispersions of surfactant with a fixed amount of
1.8% (w/w) particles were prepared following the same procedure
as detailed in the previous section. In this case, dispersions were
first centrifuged (Jouan Centrifuge MR1812, Kirchzarten, Germany)
at 10 000 rpm during 10 min for particles separation. Particles were
removed in order to avoid measurement disturbances as particles
attachment on the ring and to determine the surface tension of the
surfactant dispersion remaining in the bulk. Only the resulting sur-
factant solutions were analyzed. All measurements were repeated
at least three times.
2.4. Emulsion characterization
2.4.1. Stability measurements (bottle test method)
The stability of emulsions was studied using the bottle test
method by observation the sample phase separation with time.
Freshly prepared emulsions were transferred into 10 mL graduated
glass bottles sealed with a plastic cap and stored for 21 days at room
temperature (20 ± 3 ◦ C). The oil phase separation from the emulsion
was visually monitored at regular time intervals. No aqueous phase
separation was observed for all emulsions after 21 days. The per-
centage of each phase volume in relation to the total volume was
calculated. Analyses were performed in triplicate.
2.4.2. Morphology and droplet size distribution measurements
The measurements of water droplet diameters and size dis-
tributions in emulsions were performed by laser light diffraction
instrument (Mastersizer X Malvern Laser Diffraction, Worces-
tershire, UK) equipped with a lens of 100 nm permitting the
determination of sizes from 0.1 to 200 ␮m. Analyses were realized
at room temperature (20 ± 3 ◦ C) right after emulsions preparation.
A small quantity (0.05–0.1 mL) of emulsion was introduced in a
sample dispersion unit (100 mL) containing the continuous phase
(pure paraffin). Diluted emulsions were put into circulation at a
constant and low flow rate of about 1 mL/min. The typical droplet
size distributions were reported and the volume particle diame-
ter (D43 ) was calculated as the mean of three readings per sample.
For the case where the dispersion of water droplets was incomplete
after emulsion dilution, the size of droplet aggregates was detected
by laser diffraction.
To complete the information obtained by laser granulometry,
the microscopic observation of emulsion morphology was done
using an optical microscope. A drop of freshly prepared emulsion
was placed on the glass slide and gently covered with a cover slip.
The images were processed using a Labophot-2 microscope (Nikon,
Sendai, Japan), linked to a digital video camera (ExwaveHAD, Sony,
Tokyo, Japan) at a magnification of 400×.
2.4.3. Rheological measurements
The rheological flow behavior and viscoelastic properties of
samples were measured using a controlled rate rheometer (Phys-
ica MCR 301, Anton Paar, Graz, Austria) fitted with a cone and
plate geometry with the diameter of a cone of 50 mm, the cone
angle of 1◦ . The temperature was kept at 20 ◦ C during the measure-
ments by a Paar Physica circulating bath and a controlled Peltier
system with accuracy of ±0.1 ◦ C. Samples were carefully placed on
the measuring plate and left to rest for 2 min for structure recov-
ery and temperature equilibration. Flow experiments were realized
on the oil phase or on freshly prepared emulsions with different
51
concentrations of Span® 80 for shear stress values varying from
0.001 to 1000 Pa. The flow curves containing shear rates, shear
strains and shear viscosities were established. The yield stress val-
ues were determined from a plot of shear stress as a function
of shear strain by the tangent crossover method (using two tan-
gents). Dynamic oscillatory shear measurements were used for the
frequency sweep tests. The viscoelastic linear region was deter-
mined by preliminary amplitude sweeps (0.01–100% strain, 1 Hz).
Experiment was followed by frequency sweeps ranging from 10
to 0.1 Hz at a strain of 0.05%. From these measurements, emulsion
viscoelastic parameters such as storage (G ) and loss (G ) moduli
were determined. All measurements were repeated three times
with each sample.
3. Results
3.1. Emulsion stability with time
The stability of W/O emulsions as a function of the Span® 80
concentration at constant amount of silica particles (1.8%, w/w)
was investigated using bottle test method. As shown in Fig. 1,
the evolution of systems monitored at different time intervals. For
the studied emulsions, the oil phase separation without any water
phase separation was observed up to 21 days of storage. Experi-
mental results clearly show that the phase separation was more
pronounced at high surfactant concentration. After 21 days, around
40% of oil was separated in the case of emulsion containing 1.8%
(w/w) of silica particles and 1.8% of surfactant. In contrast to this
result, the improvement in the stability of emulsion in the presence
of small amount of surfactant was noticed. No phase separation was
observed in the case of W/O emulsion stabilized by 1.8% (w/w) of
silica particles and 0.1% (w/w) of surfactant. Comparing the emul-
sions stabilized by solely silica particles with those stabilized by
the mixture of particles and surfactant, it was revealed that in the
former case the emulsions had intermediary stability (about 15% of
oil separated after 21 days) between samples containing low con-
centration of Span® 80 and those containing high concentration of
Span® 80. The same tendency was observed for the W/O emulsion
stabilized with 1.8% (w/w) of Aerosil® R711 solely in previous study
[5]. A slight difference between obtained results could be attributed
to the difference in the diameter of the dispersing element used for
emulsion preparation.
The stability tests revealed the existence of optimal surfac-
tant concentration for which a maximal emulsion stability was
observed. According to the bottle test results, the more stable emul-
sion was obtained using oil phase containing 1.8% (w/w) Aerosil®
R711 and 0.1% (w/w) Span® 80. Moreover, this sample showed a
good stability and no phase separation up to 21 days even at 45 ◦ C
(data not shown). To explain this behavior the interfacial proper-
ties, emulsion morphology, droplet size and rheological properties
of mixed emulsifier dispersions as well as W/O emulsions were
analyzed.
3.2. Interfacial properties
In order to evaluate the interaction between silica particles and
surfactant, the interfacial properties of water/paraffin oil system
were examined. Firstly, to ensure the absence of impurities in the
both oil and water phases, the water/paraffin oil interfacial tension
value of 51.6 ± 0.6 mN/m was determined, as described in previous
study [5]. Then the interfacial tension of water/oil system was mea-
sured at different concentrations of Span® 80 in paraffin oil without
particles or mixed with 1.8% (w/w) of particles. The shapes of the
plots of interfacial tension against surfactant concentration are pre-
sented in Fig. 2. The results obtained demonstrate that for the
52 A. Nesterenko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 49–57
Fig. 1. Bottle test results demonstrating phase separation as a function of time for W/O emulsions (30/70, v/v) with oil phase containing 1.8% (w/w) of Aerosil® R711 and
different concentrations of Span® 80 surfactant.
dispersions containing only Span® 80, the interfacial tension pro-
gressively decreases with increasing surfactant concentration. The
lowest value of 3.5 mN/m is observed for 0.025% (w/w). As above
this concentration the interfacial tension remained constant, it may
be concluded that the critical micellar concentration (CMC) for the
formation of inverse micelles for Span® 80 is situated between 0.02
and 0.03% (w/w). This result is in accordance with previous studies
[24–26].
A similar decrease in interfacial tension with increase of Span®
80 concentration is observed for the dispersions containing silica
Fig. 2. Evolution of water/oil interfacial tension with concentration of Span® 80
surfactant: (䊉) without silica particles and () with 1.8% (w/w) of Aerosil® R711.
particles. However, the addition of particles results in an obvi-
ous shift of the plotted curves into the range of higher surfactant
concentrations. This observation confirms the existence of strong
interactions between surfactant molecules and particles. The sur-
factant molecules would adsorb onto particles having a very large
specific area [23]. This adsorption results in the decrease of Span®
80 concentration in the bulk and at the water/oil interface. Thus, a
much higher amount of surfactant is required to decrease interfa-
cial tension and to come up to the same Span® 80 concentration in
the bulk compared to the system without particles, which explains
the shift phenomenon. As a consequence, the apparent CMC value
in presence of silica particles is significantly higher than that of
sole surfactant system: around 0.5–0.6% (w/w). This adsorption
of surfactant could modify the wettability and the hydrophobic
character of particles therefore altering the properties of formed
emulsion [22,27]. Additionally, the amount of non-adsorbed on
particles surfactant remained in oil dispersion affected the emul-
sification process and emulsion properties, as shown in the next
paragraphs.
3.3. Emulsion morphology and droplet size
To study the emulsion morphology, preparations were ana-
lyzed right after emulsification step by optical microscope. Optical
microscopy images displayed in Fig. 3 show that, at constant par-
ticle amount, the droplet size in W/O emulsions is dependent on
surfactant concentration. An important decrease in water droplet
size is observed with increasing Span® 80 concentrations. This
effect can be associated to the lower water/oil interfacial tension
which reduces the free energy required to create new interface [20].
Thus, during emulsification step the droplet break-up was favored.
A similar result was reported earlier [22] in a study dealing with
 A. Nesterenko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 49–57
Fig. 3. Optical microscopy images of W/O emulsions (30/70, v/v) with oil phase containing 1.8% (w/w) of Aerosil® R711 and different concentrations of Span® 80 surfactant.
Scale bar – 0 ␮m.
W/O emulsion stabilized by silica particles and non-ionic surfac-
tant. At the same time, the images demonstrated that emulsion
stabilized by Aerosil® R711 solely has an intermediate droplet size
between samples with low and high Span® 80 concentration.
Additionally, microscopic observation of the microstructure of
samples shows that droplets formed have a spherical and well
defined drop contour, except for samples with low surfactant
concentration (0.1–0.2%, w/w). For these emulsions, more closely
packed aggregates of fine droplets are formed around the large
droplets. This flocculation and aggregation of small droplets allows
the creation of protective layer for the big droplets.
Simultaneous measurements of the droplet size distributions
in W/O emulsions were realized by laser diffraction. The results
obtained confirmed the microscopy observations and showed the
decrease of droplet volume diameter after adding surfactant (Fig. 4).
This was demonstrated by the displacement of size distributions
toward lower values as surfactant concentration increased due
to lowering of the interfacial tension. As shown in Fig. 2, at low
Span® 80 concentration (0.1–0.2%, w/w), the majority of surfac-
tant was adsorbed on silica particles. Considering that the area
per molecule of Span® 80 is 32 Å2 /molecule [3], the amount of
Fig. 4. Droplet size distributions in volume of W/O emulsions (30/70, v/v) with oil
phase containing 1.8% (w/w) of Aerosil® R711 and different concentrations of Span®
80 surfactant.
53
surfactant remaining in the bulk was insufficient for complete
emulsion droplets coverage. Consequently, W/O emulsions stabi-
lized with the small amount of surfactant contained both large and
fine droplets. Nevertheless, from the concentration of 0.6%, w/w,
the amount of surfactant was enough to cover the totality of water
droplets.
For the emulsions analyzed, bimodal or trimodal large distribu-
tions were observed indicating the polydisperse character of the
samples, in agreement with the images from optical microscopy.
Moreover, the difference in morphology of emulsions (presence
of flocculated droplets at low surfactant ratio) observed by opti-
cal microscopy affects the mean droplet size. The largest size
of droplets was obtained for the samples with silica particles
and 0.1% (w/w) of surfactant. The mean droplet size varies from
34.1 ± 1.5 ␮m to 4.4 ± 0.7 ␮m for the emulsions containing 0.1%
(w/w) and 1.8% (w/w) of Span® 80, respectively. In the case of W/O
emulsion stabilized solely by 1.8% (w/w) Aerosil® R711, a mean
droplet size of 12.8 ± 0.2 ␮m was obtained. As was shown in our
previous study [5] the droplet size distribution for the emulsion
prepared with 1.8% (w/w) of Span® 80 was centered on around
1.5 ␮m.
3.4. Rheological characterization
3.4.1. Flow behavior
The rheological behavior of continuous oil phase and W/O emul-
sions with different emulsifier compositions was investigated using
flow experiments to understand the macroscopic mechanism of
stabilization. The amount of Aerosil® R711 silica particles was fixed
at 1.8% (w/w) for all systems studied. The concentration of Span®
80 surfactant was varied from 0 to 1.8% (w/w).
As shown in Fig. 5, the rheological curves obtained for all studied
systems are characterized by a yield stress, contrary to the lin-
ear curve of pure paraffin oil that evidences a Newtonian behavior
[28–30]. Below certain applied stress these samples demonstrated
elastic properties as a solid, but flow like a fluid for threshold above
the yield stress value [28,31,32], typical of a gel-like structure. The
results indicate that the Aerosil® R711 silica particles behave like
54 A. Nesterenko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 49–57
Fig. 5. Stress–strain plots of paraffin oil dispersions (open symbols) and correspond-
ing W/O emulsions (30/70, v/v, filled symbols) with oil phase containing 1.8% (w/w)
of Aerosil® R711 (/䊉) without Span® 80, (/) with 0.1% (w/w) of Span® 80 and
(/) with 1.8% (w/w) of Span® 80. The solid line corresponds to pure paraffin oil.
a thickening agent of paraffin oil by the formation of a 3D net-
work in the bulk phase, as it was suggesting in our previous article
[5]. However, a modification of the rheological profile is observed
depending on the Span® 80 surfactant concentration.
The oil dispersion containing only silica particles is character-
ized by the yield stress of 0.4 ± 0.09 Pa compared to 0.23 ± 0.04 Pa
for the oil dispersion with particles and 0.1% (w/w) of Span® 80
(Fig. 5, open symbols). In agreement with the literature, the addi-
tion of surfactant can lead to the breakup of silica particle network
[19], resulting in a decrease of the yield stress when surfactant
concentration increases, which explains the observed behavior. On
the other hand, the rheological profiles obtained for corresponding
W/O emulsions are slightly different. The curves obtained for cor-
responding W/O emulsions (Fig. 5, filled symbols) show that the
dependence of yield stress values is permuted and the emulsion
stabilized by particles and 0.1% (w/w) of surfactant needs the high-
est stress (5 ± 0.2 Pa) to flow like a fluid. The emulsion stabilized
by silica particles solely has an intermediate behavior and a yield
stress of 2.3 ± 0.08 Pa. The emulsion containing particles and 1.8%
(w/w) of surfactant is characterized by the lowest yield stress of
0.37 ± 0.05 Pa.
The viscosity profiles of oil dispersions (open symbols) and
corresponding W/O emulsions (filled symbols) with different sur-
factant concentrations at intermediate shear rate domain are given
in Fig. 6. The results demonstrate that oil dispersions are less
viscous compared to corresponding W/O emulsions. The lowest
viscosity for each system was obtained at 1.8% (w/w) of surfactant.
Similarly to Fig. 5, for oil dispersions the sample without surfactant
is the more viscous, whereas for emulsions the sample containing
0.1% (w/w) of surfactant and 1.8% (w/w) of particles has the high-
est viscosity. The viscosity of emulsions decreases with increasing
shear rate, showing their pseudoplastic (or shear-thinning) behav-
ior [28,33]. By the application of shear forces, the gel-like structure
is partially broken and droplets move away from each other. This
shear-thinning behavior is characteristic for emulsions stabilized
with solid particles [30,34–36].
3.4.2. Viscoelastic properties
The viscoelastic characteristics of freshly prepared emulsions
were investigated by dynamic oscillatory rheology. From the vari-
ations of storage modulus G and loss modulus G it is possible to
characterize the strength of network structure of a sample. Stor-
age modulus defines the magnitude of energy stored in the sample,
Fig. 6. Shear rate dependent viscosity profiles of paraffin oil dispersions (open sym-
bols) and corresponding W/O emulsions (30/70, v/v, filled symbols) with oil phase
containing 1.8%, w/w of Aerosil® R711 (/䊉) without Span® 80, (/) with 0.1%
(w/w) of Span® 80 and (/) with 1.8% (w/w) of Span® 80.
whereas loss modulus characterized energy loss due to viscous dis-
sipation [37]. Thus, viscous properties of sample dominated at G
lower than G and elastic properties dominated at G greater than
G . G (filled symbols) and G (open symbols) of emulsions and
paraffin oil dispersion containing 1.8% (w/w) of Aerosil® R711 are
plotted against strain amplitude in Fig. 7.
The rheological profiles obtained show that storage and loss
moduli are independent of applied strain in low strain range indi-
cating the linear viscoelastic region [29]. G is greater than G for
all samples studied confirming the viscoelastic solid behavior with
gel-like structure. Comparing profiles of studied samples, the low-
est moduli values are obtained for oil dispersion containing 1.8%
(w/w) Aerosil® R711. Maximal storage modulus values (45–55 Pa)
are observed for the emulsion stabilized with particles solely and
for emulsion stabilized with 1.8% (w/w) of particles and 0.1% (w/w)
of surfactant. The increase of surfactant amount up to 1.8% (w/w)
leads to a low storage modulus value of 20 Pa.
Beyond a critical value of strain, a significant decrease of both
moduli is observed suggesting that the network structure starts
rearranging. At high strain applied, samples showed viscous liquid-
like behavior (G < G ). The transition from solid-like (G > G ) to
liquid-like (G < G ) behavior indicates the destruction of the net-
work [38]. The highest shear strain of 75% needed to break down
the emulsion structure is observed in the case emulsion containing
silica particles and a low concentration of 0.1% (w/w) of surfactant.
While for other emulsions, network structure was weaker allow-
ing an easier rearrangement to accommodate the strain. The lowest
shear strain value of 6% needed for the destruction of emulsion
network is obtained at 1.8% (w/w) of particles and high surfactant
concentration (1.8%, w/w).
In order to investigate the viscoelastic behavior of emulsion,
frequency sweeps were conducted at a fixed strain of 0.05%. The
emulsions studied exhibit the solid-like behavior with G higher
than G over the entire tested frequency range (Fig. 8). The same
observations on the effect of the surfactant concentration are
noticed.
These rheological results first indicate that the presence of
droplets in emulsion reinforced the network structure of oil dis-
persions. However, the gel-like structure of emulsions stabilized
by silica particles is depending on the Span® 80 concentration. In
agreement with the flow behavior, a high Span® 80 concentration
weakens the gel-like structure while a low Span® 80 concentra-
tion strengthens it, in comparison to emulsion stabilized solely
 A. Nesterenko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 49–57 55

Fig. 7. Strain amplitude dependence of the storage modulus G (filled symbols) and loss modulus G (open symbols) of (♦/) paraffin oil dispersion containing 1.8% (w/w)
of Aerosil® R711 and W/O emulsions (30/70, v/v) with oil phase containing 1.8% (w/w) of Aerosil® R711 (/䊉) without Span® 80, (/) with 0.1% (w/w) of Span® 80 and
(/) with 1.8% (w/w) of Span® 80.

with silica particles. Moreover, the rheological characterizations

are in good concordance with stability tests showing an interme-
diate stability of emulsion without surfactant (stabilized by 1.8%,
w/w, of silica particles) between samples with low and high Span®
80 concentrations.

4. Discussion

Surprisingly, the different results show that a low amount of

Fig. 8. Frequency dependence of the storage modulus G (filled symbols) and loss
modulus G (open symbols) of W/O emulsions (30/70, v/v) with oil phase containing
1.8% (w/w) of Aerosil® R711 (/䊉) without Span® 80, (/) with 0.1% (w/w) of
Span® 80 and (/) with 1.8% (w/w) of Span® 80.
Span® 80 surfactant seems to improve the stability of emulsion
stabilized by Aerosil® R711 silica particles. It is assumed that, in
the absence of surfactant, silica particles create a steric protective
shield for emulsion droplets [39]. Moreover, due to strong cohesive
interaction between silica particles, agglomerates of particles lead
to the formation of a 3D network in the continuous phase, which
offer a good stability to emulsion [5].
Once an amount of Span® 80 is added, interfacial mea-
surements show that surfactant molecules are adsorbed on the
particle surface. At high Span® 80 concentration, enough surfactant
molecules may screen the cohesive interactions between silica par-
ticles allowing the particle network redispersion [12]. The results
obtained by rheological measurement confirmed this tendency and
showed a weak association of emulsion system stabilized by 1.8%
(w/w) of Aerosil® R711 and 1.8% (w/w) of Span® 80. The change
56 A. Nesterenko et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 49–57
in the 3D particles network structure, in presence of Span80, is the
result of the sedimentation of the emulsion and the separation of
the oil phase. Pichot et al. [40] note that at high surfactant concen-
trations, the structure of mixed-emulsifier emulsions is very similar
to that of emulsions stabilized by surfactant alone. Dutschk et al.
[14] affirmed that in presence of solid particles surfactant can act as
a plasticizing agent increasing the fluidity of emulsion and reducing
the strength of the 3D network between droplets.
In the case of a small addition of Span® 80 surfactant, a compet-
itive adsorption of the surfactant molecules exist on the particles
surface and at the W/O droplet interface. The presence of surfactant
molecules favors the formation of small droplets during emulsifi-
cation process. But at the same time, the interfacial tension was
remained high, and relatively large droplets are also formed in
emulsion. As shown in optical microscopy images, the fine droplets
can flocculate and form bridges between neighboring large drops.
Consequently, the stabilizing network in the emulsion is formed
by both fine droplets and silica particles. Proposed explanation
is in very good agreement with the results reported by Zou et
al. [22]. Authors confirmed that the polydisperse droplet distri-
bution and the simultaneous presence of big and fine droplets
are particularly important to allow a long-term stability of W/O
emulsions stabilized by dual particle/surfactant emulsifier sys-
tem. The formation of such network structure caused thickening
of the continuous phase, provided enhanced resistance to coales-
cence of emulsion and resulted in its excellent long-term stability.
Macierzanka and Szelag [41] demonstrated that rheological prop-
erties of W/O depended on the emulsion droplet size. Large droplet
emulsion contained higher amount of non-adsorbed solid particles
acting as shear-thinning agent which resulted in higher emulsion
yield stress.
Comparing to our previous results dealing with W/O emulsion
stabilized by Aerosil® R711 or Span® 80 [5], present study suggests
that for the maximal emulsion stability the use of combination of
particles and small amount of surfactant was the most preferred
compared to each emulsifier alone. The dual emulsifier system
allowed the synergic stabilization of emulsion. The research of
Binks et al. [12] confirmed a crucial role of the synergism between
surfactant and particles in the emulsion stabilization. Only in the
case of mixed emulsifier system with particles and surfactant a
suitable quality of emulsions in terms of stability was obtained.
5. Conclusion
This study developed the use of double emulsifier system con-
taining silica particles Aerosil® R711 and non-ionic surfactant
Span® 80 for water-in-oil (W/O) emulsion stabilization. The influ-
ence of surfactant concentration at constant amount of particles on
emulsions properties was particularly investigated. The existence
of interactions between particles and emulsifier was evidenced by
interfacial tension measurements. As a result, the CMC value for
mixed-emulsifier system was significantly increased compared to
surfactant alone. The raise in surfactant concentration resulted in
the reduced emulsion droplet size which was revealed by opti-
cal microscopy and laser diffraction measurements. Moreover, the
presence of closely packed aggregates around the large droplets
was observed in the case of emulsion stabilized by small amount
of surfactant (0.1%, w/w) and particles. This emulsion remained
with highest stability up to 21 days without any phase separation.
While the emulsions with 0 or 1.8%, w/w of surfactant and par-
ticles showed significantly lower stability. Thus, an optimal W/O
emulsion stabilization was achieved at low surfactant concentra-
tion. The oscillatory tests showed that W/O emulsions exhibited
solid-like behavior over the entire tested frequency range. At 0.1%
(w/w) of surfactant, the shear strain value needed to break down
the emulsion structure was particularly high, confirming the strong
association of droplets in emulsion. A possible explanation for this
phenomenon could be the formation of particular stabilizing net-
work in the emulsion using both fine droplets and silica particles.
Such network structure allowed thickening of the oil continuous
phase improving the strength of emulsifier tridimensional network
structure and stability of emulsion. The results of this paper con-
tributed to a better understanding of W/O emulsion stabilization
mechanism using mixed particle/surfactant emulsifier system.
Acknowledgements
The European Space Agency is gratefully acknowledged for the
financial support from the MAP-projects FASES (Fundamental and
Applied Studies of Emulsion Stability) and PASTA (Particle Stabi-
lized Emulsions and Foams).
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