Colloids and Surfaces A: Physicochem. Eng.

Aspects 365 (2010) 171–177

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

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

Evolution of water-in-oil emulsions stabilized with solid particles

Influence of added emulsifier
Audrey Drelich, François Gomez, Danièle Clausse, Isabelle Pezron ∗
Groupe Interfaces et Milieux Divisés, EA 4297 Transformations Intégrées de la Matière Renouvelable,
Université de Technologie de Compiègne, BP 20529, 60200 Compiègne Cedex, France

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

Article history: Water-in-oil emulsions made of water droplets dispersed in a continuous paraffin oil phase were pre-
Received 30 October 2009 pared and stabilized with hydrophobic silica particles alone. Differential scanning calorimetry (DSC)
Received in revised form 15 January 2010 experiments were carried out to characterize the water droplets freezing transitions and their evolution
Accepted 19 January 2010
with time. Water droplet size distribution, oil–water interfacial tension, and rheological stress–strain
Available online 25 January 2010
properties were determined alongside to better understand the role of particles in the formation and
stabilization of emulsions. The results obtained were compared to the properties of emulsions prepared
Keywords:
with a non-ionic emulsifier, sorbitan monooleate. No interfacial tension reduction was observed at the
Solid-stabilized water-in-oil emulsions
Differential scanning calorimetry
oil/water interface in presence of particles. As a consequence, the fragmentation of water into droplets
Water droplet crystallization required more energy in absence of surface-active emulsifiers. The resulting emulsion droplet size dis-
Rheology tribution is polydisperse and contains large droplets. Rheology measurements showed that the stability
Laser diffraction of the emulsion prepared with particles originates from the formation of a 3D network of particles in
Droplet size distribution the continuous oil phase. In emulsion samples containing sorbitan monooleate, calorimetry experiments
Emulsion stability revealed a progressive displacement of the water droplet freezing transition due to a change in ice nucle-
ation mechanism. The interpretation points out a possible reorganization of the emulsifier film at the
water/oil interface, which could modify the conditions of crystallization of dispersed water droplets and
affect the emulsion long-term stability. Calorimetry, when used together with other techniques, such as
laser light scattering, provides complementary information on the evolution with time of the structure
of the emulsion.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction change, due to reversible or irreversible mechanisms [5]. Reversible

Solid-stabilized emulsions have received a lot of attention
recently as the replacement of surface-active emulsifiers by solid
particles is considered to improve their long-term stability [1–3].
However the mechanism of emulsion stabilization by solid parti-
cles, and their interaction with surface-active material is no fully
understood [4].
Emulsions are unstable systems which ultimately evolve
towards the separation of the oil and water phases. For manufac-
tured emulsions, the challenge is to control the system stability and
avoid its destabilization during storage, for instance when environ-
mental conditions, such as temperature, change. Conversely, for
natural emulsions, as petroleum emulsions formed during crude-
oil extraction, destabilization of the system and separation of the
two phases is generally required. With time, the distribution of
water droplets in the continuous oil phase of the emulsion will
∗ Corresponding author. Tel.: +33 3 44 23 46 18; fax: +33 3 44 23 19 80.
E-mail address: isabelle.pezron@utc.fr (I. Pezron).
mechanisms include sedimentation of the water droplets and
partial separation of the oil phase, which happen without any
modification of the droplet size distribution. Homogenization of
the system usually restores the initial appearance of the emul-
sion. Flocculation will also be observed when droplets, which are
in constant motion, come close to each other and aggregate. The
absence of strong repulsive forces in the continuous oil phase
may promote droplet aggregation. Flocculation can be reversible
or quasi-irreversible depending on the interaction forces between
the droplets [6]. Irreversible flocculation may ultimately lead to
the coalescence of the droplets following the weakening of the
interfacial film. In this case, the droplet size distribution is affected
and progressively shifted towards larger droplet sizes. Another
irreversible destabilization mechanism is Ostwald ripening [7], in
which a transfer of water from the smaller to the larger droplets is
observed due to differences in water chemical potential. This effect
is due to capillary phenomena and occurs for droplet size less than
1 ␮m. All these mechanisms may take place simultaneously, which
makes the understanding and modelling of emulsion destabiliza-
tion very challenging, particularly in the case of multi-component
emulsions.

0927-7757/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2010.01.042
172 A. Drelich et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 365 (2010) 171–177
A common way to study the emulsion destabilization mech-
anisms is to follow the evolution of the droplet size distribution
with time. Different techniques may be used for this purpose. Opti-
cal techniques allow direct measurement of droplet size, but they
require a dilution of the emulsion, in particular for opaque and
concentrated systems. Another way to obtain information on the
water droplet dispersed state without any dilution of the system
is by using differential scanning calorimetry (DSC) [8]. This tech-
nique allows the detection of freezing and melting transitions of
dispersed water droplets. Freezing of water droplets is a stochas-
tic process which depends on several parameters, including ice
nucleation mechanism, droplet volume or cooling rate [8,9]. This
phenomenon leads to undercooling state of water and freezing
temperatures which are well below the liquid/solid equilibrium
temperature. When droplets are of micrometric size, and well
isolated from each other, homogeneous nucleation processes are
usually observed [8,9]. In this case, droplets will freeze at a tem-
perature which depends on the droplet volume and on the cooling
rate. Indeed, it has been shown in previous studies that the degree
of undercooling decreases when the droplet volume increases and
when the cooling rate decreases [10–12]. For instance, droplets
of size 1 ␮m will be typically characterized by a “most probable”
freezing temperature close to −40 ◦ C. When nucleating agents, or
ordered amphiphilic monolayers are present in the system, a dif-
ferent nucleation mechanism, heterogeneous nucleation, may take
place [13]. For instance, crystallization of ice can be triggered by
the presence of silver iodide crystals, or bacteria, which offer a good
structural match with ice crystalline structure [14]. In other cases,
the presence of condensed Langmuir monolayers has been shown
to induce water crystallization at the oil/water interface [13,15].
In the case of heterogeneous nucleation, freezing temperatures are
closer to the water/ice equilibrium temperature. For instance, in
presence of silver iodide, the freezing temperature of emulsified
water has shifted from −40 ◦ C to −22 ◦ C [14].
The work presented here deals with water-in-oil (W/O) emul-
sions prepared solely with hydrophobic fumed silica nanoparticles.
To better understand the role of the particles in the formation
and stabilization of emulsions, water droplet size distribution,
oil–water interfacial tension, and rheological stress–strain proper-
ties were determined and compared to the properties of emulsions
prepared with a non-ionic emulsifier, sorbitan monooleate. The
stability of the emulsions was studied by following, on the same
systems, the evolution of the droplet size distribution with time,
and the displacement of freezing/melting transition of dispersed
water droplets. The influence of added emulsifier on the evolution
of the emulsion stabilized with particles was also studied in order
to investigate the competitive role of particles and emulsifier in
the stabilization of water-in-oil emulsions. In this case, emulsifier
molecules were added after the emulsification process in order to
keep the droplet size distribution unchanged.
This study was carried out in the framework of the FASES
(Fundamental and Applied Studies on Emulsion Stability) project,
supported by the European Space Agency (ESA), in which exper-
iments aiming to correlate interfacial properties and emulsion
stability are performed in ground, and under microgravity condi-
tions [16].
2. Materials and methods
2.1. Emulsion preparation
The paraffin oil used, supplied by Carl Roth GmbH (Karlsruhe,
Germany), is characterized by a low viscosity of 32cP and a
density of approximately 0.85 g/cm3 at 20 ◦ C. Ultra-pure water
(resistivity 18 M cm), used for all experiments, was produced
by a purification chain provided by Aquadem/Veolia water STI
(Wissous, France). The particles used are fumed silica from the
Aerosil® range (Aerosil® R711) supplied by Evonik Industries AG
(Rheinfelden, Germany). They consist in sintered branched net-
work, called aggregates, obtained by fusion of primary spheres
(size 12 nm) of silicone dioxide in a combustion process. Their
hydrophobic character comes from the substitution of silanol
groups by methacrylsilane moieties. The same type of particles was
used in previous studies of transfers in mixed water-in-paraffin
oil emulsions [17], and to stabilize water-in-toluene emulsions
[18]. The surface-active emulsifier used is sorbitan monooleate
C24 H44 O6 (molecular weight 428.6), also called Span® 80, supplied
by Fluka/Sigma–Aldrich Switzerland (Buchs, Switzerland). It is a
non-ionic lipophilic emulsifier of HLB 4.3. Span® 80 is a viscous liq-
uid (viscosity 1.2–2.0 Pa s), with a density equal to 0.99 g/cm3 at
20 ◦ C.
The percentage of water phase is 30 vol.% of the total volume for
all the emulsions studied, and those of particles or emulsifier are
1.8 wt% of the oil phase. The oil phase was prepared by mixing emul-
sifier or particles with paraffin oil using an Ultra Turrax T25 high
speed blender Janke&Kuntel (Staufen, Germany) homogenizer at
25,000 rpm for 5 min at room temperature. 10 g of emulsion were
prepared by slowly adding the required amount of water to the
oil phase while mixing the system using the same homogenizer at
25,000 rpm for 5 min at room temperature. To study the influence of
sorbitan monooleate on the emulsion stability, the emulsifier was
added to an initially stable emulsion prepared solely with particles.
The emulsifier was slowly mixed with the emulsion right after its
preparation (at a concentration up to 1.8 wt% of the oil phase), using
just a spatula in order to homogenize the emulsion without modi-
fication of the initial droplet size distribution. The experiment was
repeated in order to verify the reproducibility of the results.
2.2. Differential scanning calorimetry
Differential Scanning Calorimetry technique was performed
with a DSC111 Setaram calorimeter (Caluire, France) [19]. First, an
emulsion sample of about 100 mg is introduced in the calorimeter
cell at ambient temperature. Then, the calorimetric cell is placed in
the head of the calorimeter, equilibrated for 300 s at 20 ◦ C, followed
by a cooling experiment from 20 ◦ C to −60 ◦ C and heated back to
20 ◦ C, at a regularly speed of 2 ◦ C/min. For each type of emulsion,
the reproducibility was verified by studying several similar fresh
emulsions and typical thermograms are reported in the result sec-
tion. Freezing temperatures are reported as averages of at least 5
measurements. For stability studies, emulsion samples were imme-
diately introduced in calorimeter cells after emulsion preparation,
and then stored in a refrigerated chamber (temperature 20 ◦ C) until
further analysis at different time intervals.
2.3. Interfacial tension measurements
Water/oil interfacial tensions were measured at room temper-
ature (20 ± 2 ◦ C) by using a Drop Shape Analysis system Krüss
DSA10 (Hamburg, Germany). A drop of paraffin oil containing
either Span® 80 or Aerosil R711 particles was formed in water and
the shape of the emerging drop was recorded and analyzed. The
reported values are the averages of at least 5 measurements with
corresponding standard deviations.
2.4. Laser diffraction and microscopy
Droplet size distributions of emulsions were determined by
laser light scattering at regular time intervals using a Mastersizer X
Malvern Laser Diffraction (Worcestershire, England) with a lens of
100 nm to measure sizes between 0.1 and 200 ␮m. Measurements
 A. Drelich et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 365 (2010) 171–177
were performed at room temperature at 20 ± 2 ◦ C. Emulsion
samples were diluted in a sample dispersion unit of 100 mL
containing pure paraffin oil, and put into circulation with a flow of
about 1 L/min. For each kind of emulsion, the reproducibility was
verified from several measurements performed on 3 different fresh
emulsions and typical droplet size distributions were reported.
In addition, emulsions were observed with a Labophot-2 Nikon
optical microscope (Japan) equipped with an ExwaveHAD Sony
color video camera (Japan), which allowed an estimation of their
droplet size. Emulsion samples were covered with a cover glass
slide to optimize the optical observation. It was verified that this
operation did not induce a modification of the droplet diameter. In
the case of phase separation, samples were withdrawn within the
emulsion phase.
2.5. Rheological measurements
Rheological behaviors of oil phases and water/oil emulsions
containing various emulsifier or particle concentrations were
determined by creep tests. Measurements were carried out at 20 ◦ C
by using a RS600 Haake Thermo Electron Rheometer (Karlsruhe,
Germany) with a cone-plate geometry characterized by a diameter
of 60 mm and a cone angle of 1◦ , and connected to a Peltier system
of temperature regulation to maintain the sample temperature at
20 ◦ C. First, samples of approximately 4 mL were put down on the
plate at rest during 900 s. Then, shear strain was measured while
shear stresses were increased step by step from 0.001 to 10 Pa (each
step lasts 60 s). Yield stresses were determined at the rupture and
the reported values are the average of at least 3 measurements with
the corresponding standard deviation.
2.6. Bottle test
A rapid indication of emulsion stability was given by the bot-
tle test method by monitoring the extent of phase separation with
time. Emulsions were placed in 10 mL graduated glass test tubes
and stored at 20 ◦ C in a refrigerated chamber. The volume of sepa-
rated oil was measured at regular time intervals. The percentage of
each phase (emulsion, oil phase, water) was reported as a function
of time for up to 21 days.
Emulsion stability was also studied by following the evolution,
with time, of the droplet size distribution by laser diffraction, and
by monitoring the displacement of the freezing transition of the
water droplets by DSC. In that case, emulsion samples were imme-
diately introduced in calorimeter cells after emulsion preparation,
and then stored in a refrigerated chamber (temperature 20 ◦ C) until
further analysis at different time intervals.
3. Results and discussion
3.1. Emulsion characterization by DSC
The thermograms obtained during cooling and heating of an
emulsion sample are reported on Fig. 1. Calorimetric analysis of
pure paraffin oil was also performed using the same protocol and
reveals a glass transition of paraffin oil at a temperature of about
−12 ◦ C. Emulsion stabilized by Span® 80 is characterized by a water
solidification peak centered around −39.2 ± 0.7 ◦ C (average of 6
experiments). This signal is typical of the crystallization of small
␮m-sized water droplets [8,10]. In the case of emulsions prepared
with R711 particles, the thermogram indicates a large solidi-
fication peak around −37.2 ± 0.4 ◦ C (average of 6 experiments)
together with very small peaks observed at higher temperatures.
The high degree of undercooling of pure water, observed in both
cases (T ≈ +39 ◦ C and +37 ◦ C) is characteristic of homogeneous
173
Fig. 1. Typical thermograms with solidification signals of water-in-paraffin oil
emulsions (30/70 in volume) stabilized by 1.8% of emulsifier or 1.8% of silica particles
in weight.
nucleation of ice in emulsion droplets [10,11,13]. The equilib-
rium solidification temperature of water is 0 ◦ C under atmospheric
pressure. We can conclude from these results that the emulsions
formed are water-in-oil emulsions in both cases. The small differ-
ence between the temperatures at which the freezing transition
is observed may originate from a slight difference in the droplet
size distribution of both systems. Similar freezing temperatures
were obtained for ␮m-sized water-in-olive oil emulsion droplets
stabilized with clays [20].
In order to better characterize the emulsions obtained, and
understand the role of the particles in the formation and stabiliza-
tion of the emulsions, water droplet size distribution, oil–water
interfacial tension, and rheological stress–strain measurements
were undertaken. The results are presented in the next sections.
3.2. Interfacial properties
First, water/air and paraffin oil/air surface tensions as well as the
water/paraffin oil interfacial tension without emulsifier or particles
were measured to ensure the absence of surface-active impurities
in the oil phase. Values of  w = 72.7 ± 0.2 mN/m at the water/air
interface,  o = 30.3 ± 0.2 mN/m at the paraffin oil/air interface and
 w/o = 51.7 ± 0.6 mN/m at the water/paraffin oil interface were
obtained as an average of 3 experiments. The water/paraffin oil
interfacial tension obtained is consistent with the value calculated
using Fowkes approach [21], by taking paraffin oil as a purely dis-
persive liquid (dispersive components of the surface tension are
taken as w d = 21.8 mN/m for water and  d =  = 30.3 mN/m for
o o
paraffin oil):
d 1/2
w/o = w + 0 − 2 · (w · od ) = 51.6 mN/m (1)
The water/paraffin oil interfacial tension value obtained is also
in agreement with values found in the literature [22] and confirms
that no surface-active impurities are present in pure paraffin oil.
Results of interfacial tension between water and paraffin oil
dispersions containing 1.8 wt% of solid particles or emulsifier evi-
denced a very different behavior of the two systems. With 1.8%
emulsifier in the oil phase, the interfacial tension obtained was
 = 3.3 ± 0.7 mN/m. According to Santini et al. [22], water/paraffin
oil interfacial tension progressively decreases with increasing
Span® 80 concentrations, down to 3 mN/m at a concentration
of 0.025 wt%. Above this concentration, the interfacial tension
remains constant, which suggests that the critical micellar concen-
tration (cmc) for the formation of inverse micelles has been reached
[22]. The value we obtained is therefore in agreement with this
study as the concentration of emulsifier used, i.e. 1.8%, is far above
the cmc.
174 A. Drelich et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 365 (2010) 171–177
Fig. 2. Droplet size distribution in volume of water-in-paraffin oil emulsions (30/70
in volume) containing 1.8% of emulsifier or 1.8% of silica particles in weight. Images
represent observations by optical microscopy of each system right after emulsion
formation: (a) emulsion containing 1.8 wt% of Span® 80. (b) Emulsion containing
1.8 wt% of Aerosil® R711 silica particles.
Conversely, with 1.8 wt% of Aerosil® R711 particles dispersed in
the oil phase, a value of  = 53.3 ± 1.2 mN/m was obtained, which is
not significantly different from the value obtained with pure paraf-
fin oil: no interfacial tension reduction is observed. Similar results
were obtained by Vignati et al. with silanized silica particles at
isooctane or octanol/water interface [23], which showed that even
if the particles are strongly attached to the interface, no reduction
of interfacial tension reduction was detected. Aveyard et al. [24]
observed by the pendant drop technique a spontaneous adhesion
of polystyrene particles at the octane/water interface, reducing the
interfacial tension from 51.4 to 47.7 mN/m.
In all cases, interfacial tension values in presence of particles
remain very high compared to the values obtained in presence of
emulsifier. As a consequence, the process of droplet formation dur-
ing emulsification will be impeded, as more energy will be required
to fragment water into droplets in the absence of emulsifier. The
droplet size distribution will therefore be affected, as it will be
shown in the next paragraph.
3.3. Droplet size distribution
Fig. 2 shows the droplet size distributions in volume determined
by laser diffraction for emulsions prepared with 1.8 wt% Span® 80
or R711 particles. Laser diffraction experiments were made right
after emulsion preparation. As evidenced from calorimetric experi-
ments, water-in-oil emulsions were obtained, containing dispersed
water droplets. A large droplet size distribution centered on around
1.5 ␮m is observed for the emulsion prepared with Span® 80, which
is in agreement with the picture obtained by optical microscopy
(Fig. 2). In presence of solid particles, the distribution is shifted
towards larger droplet size (mean around 10 ␮m), and also reveals
a polydisperse character as several peaks are observed. Images
from optical microscopy illustrate the polydisperse character of
the distribution, showing large globules together with a majority
of ␮m-sized globules. The calorimetric analysis of the thermogram
obtained for the emulsion prepared with R711 particles is consis-
tent with the droplet size distribution. The broad solidification peak
observed at around −37 ◦ C reflects the large distribution of droplets
sizes, which on average are bigger than the droplets formed in
presence of emulsifier.
3.4. Rheological properties
To better understand the role of the particles in the stabilization
of the emulsion, rheological properties of paraffin oil dispersions in
Fig. 3. Stress–strain curves of paraffin oil dispersions for several Span® 80 (filled
symbols) or R711 silica particles (hollow symbol) weight% (( and ) 2.4 wt%; (
and ) 1.8 wt%; ( and ♦) 1.2 wt%; (䊉 and ) 0.4 wt%). The solid line corresponds to
pure paraffin oil.
bulk were performed for several amounts of Span® 80 and Aerosil®
R711 particles. Measurements of the strain as a function of the shear
stress are plotted on Fig. 3 for both systems. Rheological properties
of pure paraffin oil were determined using the same apparatus and
protocol, and evidence a Newtonian flow behavior. In presence of
emulsifier, the curves obtained for all paraffin oil phases are linear,
and are superimposed for the range of emulsifier concentrations
investigated from 0.4 to 2.4 wt%. This result equally characterizes
a Newtonian flow profile similar to pure paraffin oil. These results
suggest that the emulsifier Span® 80 does not affect the rheological
properties of paraffin oil.
A very different rheological profile is observed with silica par-
ticles. Macroscopic considerations show that Aerosil® R711 silica
particles behave as a thickening agent of paraffin oil. Furthermore,
the curves obtained (Fig. 3) show that paraffin oil dispersions are
characterized by a yield stress. Dispersions behave as a solid under
low applied stress and may start to flow for threshold above the
yield stress value [25–27]. Moreover, the yield stress increase with
larger amounts of silica particles shows that the plastic solid flow
behavior is reinforced. Yield stress values obtained for all continu-
ous phases investigated are summarized on Table 1. These values
are relatively low, which shows that a mild stress is enough to make
the system flow. The dependence of the yield stress values on the
amount of silica particles indicates that the elastic properties of the
paraffin oil dispersions probably originate from the formation of a
network of silica particles in the bulk phase, and that the structure
is partially broken at large deformation.
Rheological properties of the corresponding emulsions were
also characterized. The results lead to the same conclusions and
even indicate an amplified effect of the silica particles on emulsion
rheological properties in comparison to paraffin oil dispersions,
due to the presence of the droplets. In addition, no destabilization
mechanisms of these emulsions, as coalescence of the droplets and
complete separation phases, were observed after shear stress cessa-
tion. This observation proves the stability of these emulsions under
flow.
Emulsion plastic behavior in presence of particles was also
observed by Sugita et al. [28] with water-in-silicone oils emul-
sions containing various amounts of hydrophobic silica particles
from 0.5 to 3 wt%, leading to yield stress values between 0.5 Pa
and 5 Pa. Binks et al. [29] obtained yield stress values ranging
between 0.01 Pa and 4 Pa with water-in-toluene or isopropyl myris-
tate emulsions stabilized by hydrophobic bentonite particles. Such
behavior was also reported by Midmore [30] with direct highly con-
centrated paraffin oil-in-water emulsions stabilized by flocculated
colloidal silica using a co-emulsifier, and characterized by a high
 A. Drelich et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 365 (2010) 171–177 175

Table 1
Yield stress values of paraffin oil dispersions and W/O emulsions for several emulsifier or fumed silica particles weight%.

Span® 80 or R711 particles (wt%) Yield stresses/Pa

Paraffin oil + Span® 80 Paraffin oil + R711 particles Emulsion containing Span® 80 Emulsion containing R711 particles

0 0 0 – 0
0.4 0 0.02 ± 0.007 0 0.1 ± 0.07
1.2 0 0.08 ± 0.01 – 0.25 ± 0.07
1.8 0 0.26 ± 0.1 0 0.75 ± 0.15
2.4 0 0.32 ± 0.08 0 1.3 ± 0.05

Fig. 4. Bottle test results showing phase separation observed as a function of time for water-in-paraffin oil emulsions (30/70 in volume) containing 1.8% of Span® 80 emulsifier
or 1.8% of Aerosil® R711 particles in weight from t = 0 to t = 21 days.

yield stress value of 150 Pa or 75 Pa, depending on the geometry

used for the measurements.

3.5. Emulsion stability with time

Emulsion stability was first assessed by monitoring the phase

separation of water-in-oil emulsions by the bottle test method
(Fig. 4). Sedimentation of the emulsion and separation of the oil
phase were observed, the phenomenon being much more pro-
nounced in presence of Span® 80. No water phase separation was
noticed after up to 21 days of storage. For emulsions prepared with
R711 particles, the bottle test shows very slow oil phase separation,
up to 21 days. Aggregation of the solid particles into a network in
the oil phase, as evidenced by rheological measurements, is most
probably at the origin of this effect. At rest, the external phase of the
emulsion behaves almost as a solid phase, which prevents the sedi-
mentation of the water droplets. In the case of emulsions containing
Span® 80, bottle test experiments evidence continuous evolution of
separation phase up to around 45% of oil separated after 21 days.
No separation of water is observed. Consequently, as the volume
of the emulsion phase is greatly reduced, the water droplets will
be much closer to each other (the volume of the dispersed phase
reaches 44 vol.%).
The evolution of both systems with time was followed simulta-
neously by DSC analysis and laser diffraction for up to 21 days. The
results obtained are gathered on Figs. 5 and 6. Thermogram analysis
of emulsions prepared with R711 particles indicates no evolution
of the solidification peaks for up to 21 days (Fig. 5a). The main sig-
nal remains at around −37 ◦ C. In the same time, results obtained
Fig. 5. Stability versus time studies of water-in-paraffin oil emulsions (30/70 in vol-
by laser diffraction show no evolution of the droplet size distribu-
ume) prepared with 1.8% of silica particles Aerosil® R711 in weight. (a) Evolution of
tion with time (Fig. 5b). Water-in-paraffin oil emulsions stabilized solidification peaks thermograms from t = 0 to t = 21 days. (b) Evolution of the droplet
by Aerosil® R711 particles are therefore characterized by a good size distribution in volume from t = 0 to t = 21 days. Images represent observations
stability versus time, with no change in droplet size. by optical microscopy of each system at (i) t = 0 and (ii) t = 21 days.
176 A. Drelich et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 365 (2010) 171–177

tallization in bulk. No such effect has been observed in absence of

Fig. 6. Stability versus time studies of water-in-paraffin oil emulsions (30/70 in
volume) prepared with 1.8% of emulsifier Span® 80 in weight. (a) Evolution of solid-
ification peaks thermograms from t = 0 to t = 21 days. (b) Evolution of the droplet
size distribution in volume from t = 0 to t = 21 days. Images represent observations
by optical microscopy of each system at (i) t = 0 and (ii) t = 21 days.
Span® 80 molecules, i.e. in the case of water and pure paraffin oil
interface or with paraffin oil containing silica particles.
The modification of structure of the emulsifier layer at the
water/oil interface may also have an influence on the stability of
the emulsion, which shows progressive destabilization and coa-
lescence with time. Our results suggest that DSC experiments
were able to detect a change in the emulsion interfacial structure,
which could have important consequence for emulsion stability,
before any modification in droplet size is observed. However, in
order to better interpret the phenomenon observed, it is necessary
to concurrently undertake experiments by complementary tech-
niques, as laser scattering experiments and observations by optical
microscopy of the emulsion.
The effect of Span® 80 molecules on stable emulsions prepared
with solid particles was also studied in order to further investigate
this destabilization mechanism. Fig. 7 shows the results obtained
by DSC analysis, laser diffraction and optical microscopy for up to
21 days. The origin of time corresponds to the moment at which
the emulsifier was added to the emulsion. During the first week, at
least, the emulsion appears to behave as the emulsion stabilized by
particles only. There is no displacement of the freezing transition
and only a small increase in particle average size. For longer times,
starting after 14 days (Fig. 7a), a second peak appeared at around
−22 ◦ C, which continuously increases with time, showing that
more and more dispersed water is concerned by this phenomenon.
Simultaneously, we observed that the water/paraffin oil interface
slowly becomes opaque when Span® 80 is added to the paraffin oil
dispersion containing particles. However, the opacity is only visible
after 13–15 days instead of 24 h for the system without particles,
showing that the buildup of multilayers at the interface takes
more time in presence of particles. This phenomenon is therefore

In the case of emulsion containing Span® 80, DSC analysis reveals

a shift in the solidification peak, from −39.2 ◦ C to −18.1 ± 1 ◦ C (aver-
age of 6 experiments) after 24 h of storage at 20 ◦ C, followed by no
further evolution (Fig. 6a) up to 21 days. A small peak at around
−39 ◦ C is still visible after 24 h and progressively disappears with
time. Simultaneous measurements of the droplet size distribution
indicate an evolution from a homogeneous distribution of very
small droplets of about 1–2 ␮m to a multimodal distribution with
an average size of 8–9 ␮m after 21 days (Fig. 6b). Images also reveal
the presence of larger droplets after 21 days, probably resulting
from the coalescence of smaller droplets. However, after 24 h, the
morphology of the emulsion has hardly changed, the average size
having only slightly increased from 1.5 to 2 ␮m. This droplet size
evolution cannot, by itself, explain the displacement of the water
solidification peak to −18 ◦ C.
A stated in the introduction part, a significant reduction of
undercooling leading to a freezing temperature around −20 ◦ C can
be observed when heterogeneous nucleation of ice occurs [11,13].
Crystallization of ice can be triggered by the presence of nucleating
agents, but also by ordered amphiphilic monolayers at the oil/water
interface [13,15]. Sorbitan monooleate molecules are known to
undergo interfacial molecular arrangements which can be due to
reverse micelles [31], or multilayer formation [32]. A viscoelas-
tic structure slowly builds up at the oil/water interface, and this
effect is particularly pronounced when an excess of emulsifier is
present [32]. At the same time, macroscopic observation of the
water/paraffin oil interface in presence of Span® 80 also reveals
an evolution of the interface aspect, which becomes progressively Fig. 7. Stability versus time studies of water-in-paraffin oil emulsions (30/70 in vol-
opaque with time. Such modification of the interface may influ- ume) prepared with 1.8% of silica particles Aerosil® R711. 1.8% of emulsifier Span® 80
in weight was added after emulsion preparation. (a) Evolution of solidification peaks
ence the mechanism of ice nucleation at the oil/water interface.
thermograms from t = 0 to t = 21 days. (b) Evolution of the droplet size distribution in
This hypothesis has to be verified, and further studies will include volume from t = 0 to t = 21 days. Images represent observations by optical microscopy
the direct evaluation of the effect of emulsifier film on water crys- of each system at (i) t = 0 and (ii) t = 21 days.
 A. Drelich et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 365 (2010) 171–177
delayed compared to what was observed with Span® 80 only, as
is the displacement of the freezing peaks. The two phenomena
seem strongly connected. Only a small evolution of the droplet
size distribution is observed at longer times (Fig. 7b), showing
that although the emulsifier adsorbs and progressively forms a
condensed layer at the oil/water interface, solid particles present in
the continuous phase may still act as a steric barrier to coalescence.
4. Conclusion
In this paper, the systematic characterization of W/O emul-
sions prepared with an amphiphilic emulsifier, Span® 80, or with
only hydrophobic silica particles, Aerosil® R711, and their evolution
with time were undertaken with complementary techniques. This
study evidenced many differences observed between both systems.
Contrary to emulsifiers, the particles do not reduce the oil/water
interfacial tension. The process of droplet formation is therefore
not facilitated by the presence of particles, and as a consequence, a
polydisperse size distribution with a significant fraction of large
droplets is obtained. However, the particles efficiently stabilize
the emulsion droplets by creating a 3D network in the continuous
phase, as evidenced by rheological studies. For up to 21 days, the
emulsion prepared with solid particles showed no sign of destabi-
lization. On the other hand, several destabilization processes were
detected on the emulsion prepared with Span® 80 alone. After only
24 h, there is a marked displacement of the freezing transition of the
dispersed water droplets although no significant change in droplet
size distribution is observed. A possible explanation would be a
change in the structure of the emulsifier layer at the interface,
inducing water crystallization with a reduced degree of undercool-
ing, as it was observed in other studies with Langmuir monolayers
at the oil/water interface. This change in structure could be at the
origin of the coalescence process observed at longer times. When
Span® 80 is added to an initially stable emulsion prepared with
particles only, a slow destabilization is observed. Both the dis-
placement of the freezing transition and a rearrangement of the
emulsifier interfacial layer are observed, but with a significant delay
(of at least 10 days), compared to the emulsion prepared with
Span® 80. The progressive replacement of particles by emulsifier
molecules at the interface could be at the origin of this effect. To
better understand the process, further work will be performed on
the specific interactions between emulsifier molecules and solid
particles, and their competitive adsorption at the paraffin oil/water
interface. All these investigations give new insight on the separa-
tion process of emulsions stabilized with particles. The calorimetry
technique is well-adapted to the study of complex and opaque
emulsion because it does not require the dilution of the emulsion
or the transparency of the system. When used together with other
techniques, such as laser light scattering, it can provide comple-
mentary information on the evolution with time of the structure of
the emulsion.
Acknowledgements
The work benefited of financial support from Région Picardie.
The European Space Agency is gratefully acknowledged for the
financial support of the MAP-project FASES (Fundamental and
Applied Studies of Emulsion Stability). Rheological studies were
carried out in the Laboratoire de Physique Pharmaceutique, Faculté
de Pharmacie (Châtenay-Malabry, France). The expertise of Jean-
Louis Grossiord and Nicolas Huang is gratefully acknowledged.
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