4316

Langmuir 2005, 21, 4316-4323

Particle-Stabilized Emulsions Comprised of Solid Droplets

J. Giermanska-Kahn, V. Laine, S. Arditty, V. Schmitt, and F. Leal-Calderon*,
Centre de Recherche Paul Pascal, CNRS, Av. Schweitzer, 33600 Pessac, France, and
Laboratoire des Milieux Disperse s Alimentaires, ISTAB,
Av. des Faculte s, 33405 Talence, France
Received January 14, 2005. In Final Form: February 8, 2005
We kinetically stabilize oil-in-water emulsions comprising paraffin crystals by adsorbing solid particles
(silica) of colloidal size at the oil/water interface. We obtain a set of emulsions that are quiescently stable
for a long period of time (months), while the same emulsions are destabilized after only a few hours in
the presence of surfactant molecules alone. The emulsions are submitted to a shear stress in order to probe
their stability under flow conditions. Partial coalescence and gelation occur when the shear is applied for
a sufficiently long period of time. The experiments reveal the existence of a critical droplet mass fraction,
*, that defines a sharp transition between slow and fast gelation. The process of gelation is rather slow
for < *, occurring at the scale of hours, and becomes almost instantaneous above *.

Introduction
It is well-known that the presence of fat crystals in the
disperse phase of oil-in-water (O/W) emulsions can cause
a significant decrease in the kinetic stability.1-4 The reason
is that crystals may protrude into the water phase, and
if such a crystal is present in the film between approaching
droplets, it may pierce the film, causing the droplets to
coalesce. The coalescence is incomplete or partial because
the network of crystals within the droplets allows the
original shape of the droplets to be maintained in the
aggregates. Partial coalescence may produce a rapid
destruction of the materials during storage and severely
restricts the application field of emulsions in which the
dispersed phase is totally or partially crystallized.
Proteins are highly efficient in stabilizing triglyceridein-water emulsions against partial coalescence and are
commonly exploited in the food industry for the preparation of dairy products. The emulsions exhibit long range
kinetic stability under quiescent storage conditions and
can even be submitted to high shear forces without being
destroyed. Instead, short surfactants generally do not
provide a sufficient degree of stabilization and the
emulsions become lumpy a few hours after their preparation. The addition of small amounts of surfactant in
protein-stabilized emulsions is a common way to monitor
the sensitivity toward partial coalescence.5-6 Small molecule emulsifiers are typically present, although they are
not required to help formulation. The displacement of
proteins from the oil interface by added surfactants
contributes to emulsion instability and induces sensitivity
to partial coalescence. In that case, shear forces due to the
processing can induce irreversible changes in the texture,
transforming the initially fluid emulsion into a rigid
material (e.g., whipped creams).
* Corresponding author. E-mail: f.leal@istab.u-bordeaux1.fr.
CNRS.
ISTAB.
(1) van Boekel, M. A. J. S. Thesis, University of Wageningen, The
Netherlands, 1980.
(2) Melsen, J. P. Thesis, University of Wageningen, The Netherlands,
1988.
(3) Boode, K.; Walstra P. Colloids Surf., A 1993, 81, 121.
(4) Boode, K.; Walstra P.; de Groot-Mosert, A. E. A. Colloids Surf.,
A 1993, 81, 139.
(5) Govin, R.; Leeder, J. G. J. Food Sci. 1971, 36, 718.
(6) Goff, H. D.; Jordan, W. K. J. Dairy Sci. 1989, 72, 18.

The present study is concerned with the development

of a different strategy to stabilize oil-in-water emulsions
comprising totally solidified droplets (paraffin). It consists
of adsorbing silica particles of colloidal size at the oil/
water interface. It is expected that the silica particles
form a rigid barrier that mechanically protects the droplets
against partial coalescence. If the characteristic thickness
of the adsorbed layer is sufficiently large compared to the
reach of the protruding crystals, these crystals should
become unable to bridge the gap between the droplets.
The main purpose of this study is to test the effectiveness
of silica particles in stabilizing emulsions made of solid
paraffin droplets dispersed in an aqueous phase.
The hydrophilic surface of the silica particles was made
partially hydrophobic by either adsorbing a small quantity
of surfactant or grafting a suitable chemical, to promote
the anchoring at the oil/water interface. We obtain a set
of model emulsions that are quiescently stable for a long
period of time (months), while the same emulsions are
destabilized after only a few hours in the presence of
surfactant molecules alone. The emulsions are then
submitted to shear forces in order to probe their stability
under flow conditions. Partial coalescence and gelation
occur when the shear is applied for a sufficiently long
period of time. We followed the kinetic evolution of the
viscosity at constant shear stress: the viscosity is weakly
varying in the first stages and suddenly undergoes a
dramatic increase. We study the influence of various
parameters on the characteristic gelation time: droplet
size, silica diameter, and paraffin mass fraction.
Materials and Methods
The dispersed phase was a paraffin wax (Merck, CAS no. 800274-2, mixture of long alkanes) with a very narrow range of melting
temperature from 42 to 44 C and a density of F ) 0.9 gcm-3.
The surfactant used was cetyltrimethylammonium bromide
(CTAB) purchased from Chempur (purity >99%). Solid-stabilized
emulsions were obtained using three different hydrophilic silica
particles (Aerosil fumed silica) provided by Degussa (France).
Their main characteristics are reported in Table 1, and we shall
refer to them as P1, P2, and P3. They were delivered in powder
form and were dispersed in pure water of Milli-Q quality under
manual shaking. It is important to note that the silica dispersions
were substantially aggregated, forming clusters at a scale of 1001000 nm in the water phase. The silica density is 2.2 gcm-3 for
all the particle types, and the specific surface areas, sp, deduced

10.1021/la0501177 CCC: $30.25 2005 American Chemical Society

Published on Web 03/29/2005

Particle-Stabilized Emulsions

Langmuir, Vol. 21, No. 10, 2005 4317

Table 1. Main Characteristics of the Particles (from

Degussa) Used in This Study (See Text for Details)
particle
name

origin

primary particle
sp
ccp
cf
diameter (nm) (m2/g) (m2/g) (m2/g)

P1
P2
P3

Aerosil A380
Aerosil A130
Aerosil Ox50

7
21
55

380
130
50

82
28
11

35
15.2
4.6

from BET adsorption isotherms (provided by the manufacturer)

are reported in Table 1.
Paraffin-in-water emulsions were fabricated in batches of 60
mL according to the following protocol. The paraffin oil (20-35
wt %) and the aqueous solution containing surfactant and/or
solid particles were heated at 60 C. The paraffin was then
deposited at the top of the water solution, and the mixture was
submitted to vigorous agitation by means of an Ultra-Turrax
homogenizer (T25 JANKE & KUNKEL) equipped with a S25
KV-25F rotor head, operating at 9000 rpm for 1 min. In the
presence of solid particles, the obtained emulsions were substantially flocculated, and very often, a thin macroscopic oil layer
appeared at the top of the samples. Homogenizing the samples
with Ultra-Turrax for a longer period of time did not change the
emulsion characteristics. This is why, right after the first
treatment, the emulsions were submitted to a second homogenization step with lower energy input. This was achieved by
means of a Rayneri mixer (Turbotest 33/300P) working at 3000
rpm for 10 min. It was not possible to produce emulsions with
an average diameter smaller than 50 m by applying this second
mechanical treatment directly. However, when associated to the
first one (Ultra-Turrax), we obtained emulsions over a wide
average diameter range (from 10 to 60 m) with enhanced
stability, since no oil leakage was observed anymore at 60 C.
Once fabricated, the final emulsions were immediately stored at
room temperature (T ) 25 C).
The emulsions were observed with a phase contrast optical
microscope (Zeiss Axiovert 100), and their size distribution
was obtained using a Malvern Mastersizer granulometer. The
size distribution was characterized in terms of the surfaceaveraged diameter

N D

N D

Ds )

and polydispersity

N D
1
i

P)

|D
h - Di|

D
h

N D
i

h is
where Ni is the total number of droplets with diameter Di. D
the median diameter, that is, the diameter for which the
cumulative undersized volume fraction is equal to 50%. Granulometric measurements were performed at T ) 25 C in a pure
water solution. The solid paraffin globules were strongly diluted
under the measurement conditions ( < 0.01%). To probe
reproducibility, several successive measurements were performed with the same sample loaded in the granulometer and
we got exactly the same size distribution. This suggests that
aggregation or partial coalescence of the paraffin droplets did
not occur in the measuring cell within the time scale of the
experiment (1 min).
Shear flow experiments were conducted at T ) 25 C with a
controlled stress rheometer (TA Instruments, AR 1000). We
adopted a thermostated Couette cell with a gap of 1 mm and
rough surfaces in order to limit wall slipping. The cell was
equipped with an antievaporating device.

Results and Discussion

1. Surfactant-Stabilized Emulsions. Figure 1 is a
microscope image of an emulsion stabilized by CTAB at

Figure 1. Microscopic image of a paraffin-in-water emulsion

stabilized by CTAB alone. T ) 25 C.

room temperature. Solidification induces a significant

change in the texture of the droplets. The spherical shape
of the warm fluid droplets which is controlled by surface
tension evolves into a rough and rippled surface due to
the formation of irregularly shaped/oriented crystals. All
the emulsions formulated with surfactants alone are
rapidly destabilized because of partial coalescence. A few
hours after the preparation, the solid droplets irreversibly
stick to each other, forming dense macroscopic agglomerates that sit at the top of the sample. The agglomerates
cannot be redispersed; instead, they form compact macroscopic clumps that totally separate from the water phase
if the emulsion is submitted to mechanical stirring.
Moreover, they melt and transform into a liquid macroscopic oil layer when the samples are reheated at 60 C.
In other words, if the aggregated system is rewarmed, the
droplets lose their integrity and fuse into a macroscopic
fluid phase, thus confirming the formation of paraffin
bridges (partial coalescence).
2. Particle-Stabilized Emulsions. 2.1. Influence of
Surfactant and Oil Contents. With the aim of improving
the stability, we emulsified the same crystallizable oil in
the presence of silica particles. Since P1, P2, and P3
particles are intrinsically hydrophilic, it was necessary to
partially hydrophobize the surfaces in order to favor
particle adsorption at the oil/water interface. To achieve
this, surfactant molecules were employed at very low
concentration. The surfactant type was adapted to obtain
the strongest anchoring of the molecules on the particle
surfaces using electrostatics. A cationic surfactant (CTAB)
was thus selected to hydrophobize the anionic P1, P2, and
P3 bare silica surfaces (pH 5-6). We observed that the
emulsions were rapidly destabilized if the surfactant
concentration initially introduced in the water phase was
above its critical micellar concentration (cmc 9 10-4
molL-1 for CTAB). It is well-known that molecules such
as CTAB form bilayers at the silica/water surface when
the free surfactant concentration in the aqueous phase
exceeds 1 cmc.7 The polar heads of the external layers are
oriented toward the water phase, and the silica surface
remains hydrophilic. Under such conditions, the solid
particles do not adsorb on the emulsion droplets and the
behavior is the same as that for surfactant-stabilized
emulsions. For initial concentrations in the water phase
lower than the cmc (cmc/5), the emulsions were kineti(7) Atkin, R.; Craig, V. S. J.; Wanless, E. J.; Biggs, S. Adv. Colloid
Interface Sci. 2003, 103, 219.

4318

Langmuir, Vol. 21, No. 10, 2005

Figure 2. Typical size distributions obtained for surfactantstabilized (dashed line) and solid-stabilized (solid line) paraffinin-water emulsions (P2 particles).

cally stable and we got experimental evidence that the

solid particles were almost totally adsorbed at the oil/
water interface. Indeed, no silica clusters were visible
under the microscope once the emulsification was achieved.
Moreover, the emulsions were stored for more than 24 h:
after that delay, the droplets formed a dense cream
coexisting with a transparent subphase. No solid sediment
was visible, thus suggesting that all the particles were
attached to the droplet interfaces. In all the experiments,
the surfactant concentration was fixed at the minimum
level required to stabilize the paraffin-in-water emulsions.
The amount of surfactant was adapted to the total mass
of particles so as to maintain the same specific coverage:
13 nm2 per CTAB molecule at the silica/water interface.
This value was estimated with the assumption that all
the surfactant from the bulk is employed to cover the silica
surface. Of course, surfactant is also adsorbed at the oil/
water interface, but in our systems, the silica surface area
is approximately 10 times larger than the droplet surface
area (deducible from eq 1 in section 2.2, with the data
given in Table 1). Moreover, the electrostatic attraction
between the oppositely charged surfactant molecules and
silica surfaces favors adsorption at the silica/water
interface.
The highest mass fraction of paraffin that can be directly
emulsified is about 35%. Above this critical value, the
final emulsions become lumpy and cannot be redispersed.
However, it was possible to get stable emulsions up to
55%, by emulsifying the oil at a lower fraction (<35%) and
allowing the droplets to cream. The emulsion viscosity
rapidly raises with the droplet fraction, and the most
concentrated samples (Ds ) 30 m, > 45%) resemble
solid pastes.
2.2. Influence of the Particle Content. We now consider
the influence of the amount of particles on the droplet size
distribution. In Figure 2, we report typical size distributions obtained for surfactant-stabilized (dashed line) and
solid-stabilized (solid line) paraffin-in-water emulsions.
The measurement for surfactant-stabilized emulsions was
carried out a few minutes after the preparation to avoid
partial coalescence. Surprisingly, the solid-stabilized
emulsions possess a relatively narrow size distribution
characterized by a low value of the polydispersity index:
P ) 0.35 ( 0.05 (see also Figure 3). Usually, emulsions
produced under turbulent flow conditions are quite
polydisperse (P > 0.5), as is the case for the surfactantstabilized emulsion shown in Figure 1.
We varied the total amount of solid particles, at a
constant mass fraction of paraffin. In Figure 4, we report

Giermanska-Kahn et al.

Figure 3. Microscopic image of a paraffin-in-water emulsion

stabilized by P2 particles. Inset: same image taken at T ) 25
C under crossed polarizers, confirming the presence of crystals
in the droplets.

Figure 4. Evolution of the inverse average diameter, 1/Ds, as

a function of the mass of solid particles employed to fabricate
the emulsion. Volume of the dispersed phase, 12 mL; total
volume, 60 mL.

the evolution of the inverse average droplet diameter as

a function of the total mass of solid particles. The linear
variation and narrow distribution suggest that the emulsions have been obtained following a limited coalescence
process.8-10 Limited coalescence occurs when a large excess
of an oil/water interface is produced, compared to the
amount that can be potentially covered by the solid
particles. When the agitation is stopped, the partially
unprotected droplets coalesce, thus reducing the total
amount of oil/water interface. Since the particles are
irreversibly adsorbed, the coalescence process stops as
soon as the oil/water interface is sufficiently covered by
the particles. For the sake of clarity, we should like to
emphasize the difference between limited and partial
coalescence. Limited coalescence occurs in the liquid state
of the droplets which recombine and freely relax their
shape. The process is interrupted after a short period of
time and leads to a dispersion of individual droplets.
Instead, partial coalescence refers to unrelaxed coalescence events that irreversibly connect the solidified
droplets through the formation of paraffin bridges.
(8) Wiley, R. M. J. Colloid Sci. 1954, 9, 427.
(9) Whitesides, T. H.; Ross, D. S. J. Colloid Interface Sci. 1995, 169,
48.
(10) Arditty, S.; Whitby, C. P.; Binks, B. P.; Schmitt, V.; Leal-Calderon,
F. Eur. Phys. J. E 2003, 11, 273.

Particle-Stabilized Emulsions

Langmuir, Vol. 21, No. 10, 2005 4319

The final average droplet diameter can be controlled by

adjusting the amount of particles. Because the solid
particles are totally and irreversibly adsorbed, the inverse
average droplet diameter, Ds, varies linearly with the
amount of particles:10

cfmp
1
)
Ds 6Vd

(1)

where mp is the mass of the particles, Vd is the volume of

the dispersed phase, and cf is the surface coverage, that
is, the amount of droplet surface area covered per unit
mass of silica. This latter quantity depends on the mixing
intensity.10 Figure 4 provides examples confirming the
validity of the previous relation. In Table 1, we report the
cf values deduced from the slope of the experimental curves
for all the particle types. For the sake of comparison, we
also calculate the theoretical surface coverage, ccp, of a
closely packed layer of adsorbed particles (2-D compacity
of 0.9): ccp ) [(x3)/8]sp. The experimental cf values are
clearly smaller than the ones calculated assuming a
densely packed arrangement. Since the particles are
initially aggregated in the continuous phase, it is likely
that clusters are attached to the surface through a reduced
number of anchoring particles and that other particles in
the clusters are protruding toward the continuous phase.
The coverage efficiency revealed by cf is thus reduced
compared to a closely packed monolayer.10,11
The silica-stabilized emulsions form networks of aggregated droplets visible under the microscope (Figure
3). The aggregates are not due to partial coalescence but
rather to an attractive interaction between the droplet
surfaces. Indeed, the clusters are labile, meaning that
they can be disrupted upon application of a shear. This
occurs, for example, if one of the glass slides that confine
the sample under the microscope is displaced with respect
to the second one. Immediately, the clusters dissociate
into individual droplets which again aggregate when the
shear is interrupted. It is worth reminding that surfactantstabilized emulsions are totally unstable upon application
of a shear.
By comparing Figures 1 and 3, it appears that the
texture of the droplet surfaces is more regular for solidstabilized emulsions than for the surfactant-stabilized
ones. We believe that the solid particles modify the crystal
size and number. Each adsorbed particle may activate
the nucleation process, and consequently, more crystals
of smaller size should be formed at the scale of the droplets.
The surfaces appear smoother because small crystals
protrude over reduced length scales.
2.3. Freeze-Thaw Stability and Resistance to Water
Elimination. An emulsion stabilized by P2 particles (Ds
) 30 m, ) 35%) was submitted to three successive
freeze-thaw cycles in order to probe its thermal stability.
It was held for 3 h at room temperature: this delay was
sufficient for crystallization to occur, as revealed by the
rippled texture of the surfaces as well as the bright spots
appearing in each droplet under light-polarized microscopy
(see inset of Figure 3). After that delay, the emulsion was
heated from 25 to 60 C (+1 C/min), maintained at 60 C
for 15 min, and cooled again (-1 C/min). No visible surface
oil was observed after the three cycles. Moreover, the
droplet size distribution was immediately measured after
each cycle and did not exhibit any variation. This definitely
confirms the absence of partial coalescence between the
paraffin droplets. These experiments also reveal the
(11) Binks, B. P.; Kirkland, M. Phys. Chem. Chem. Phys. 2002, 4,
3727.

Figure 5. Image showing the difference between a fluid

emulsion and an emulsion submitted to the water suction
experiment (see text for details). For the sake of comparison,
both samples are deposited on the same nonporous surface.
The sample on the right is the initial fluid emulsion ( ) 20%).
The sample on the left was previously deposited on a porous
substrate and became immediately solidlike.

remarkable stability of solid-stabilized emulsions with

respect to freeze-thaw cycling. As a comparison, surfactant-stabilized emulsions were almost totally destroyed
after the first cycle.
A very simple experiment was performed to qualitatively
assess the stability of solid-stabilized emulsions upon
water elimination. A 2 mL portion of emulsion at ) 20%
was deposited on a porous substrate: either a porous silica
plate or a blotting paper. Water is pumped by the substrate
under the effect of capillarity, so the droplet mass fraction
in the sample rapidly rises. Amazingly, the initially fluid
emulsion is transformed in a few seconds into a jammed
rigid material that does not flow anymore (Figure 5). We
could vary the final droplet fraction by allowing the
emulsion to reside on the porous substrate for variable
periods of time; the longer the residence time, the larger
the droplet fraction in the final state. The experiment
was carried out using an emulsion stabilized by P2
particles, with an average diameter of Ds ) 30 m. The
capillary suction provided samples with mass fractions
ranging from 50 to 60%. Each concentrated emulsion was
diluted again in pure water at about ) 5% in order to
determine whether redispersion occurs or not. Within
reasonable experimental uncertainty, it can be stated that
the samples with a volume fraction lower than (54 ( 2)%
are totally redispersable. Above that limit, irreversible
clumps were observed in the solution and the granulometric measurements revealed the presence of droplets
larger than the initial ones.
2.4. Shear Stability of Solid-Stabilized Emulsions.
Despite the aggregated structure, the emulsions were
perfectly stable with respect to partial coalescence over
several weeks at room temperature under quiescent
storage conditions. With the aim of probing the stability
under flow, the paraffin-in-water emulsions stabilized by
P1, P2, and P3 particles were subjected to shear forces
using the stress-controlled rheometer at T ) 25 C.
However, this type of experiment could not be performed
directly with the emulsions formulated according to section
2.1. Indeed, we observed rapid clumping at the emulsion/
air interface during the course of the experiments,
suggesting that the emulsion droplets have a strong
affinity toward air. Clumping was clearly initiated at the
emulsion/air interface, since no such clumps were present

4320

Langmuir, Vol. 21, No. 10, 2005

Giermanska-Kahn et al.

Figure 6. Image showing the interfacial clumping phenomenon in paraffin-in-water emulsions. The upper plate of the rheometer
was removed after shearing the sample at ) 20 Pa for 20 min. (a) Low surfactant content (13 nm2 per CTAB molecule at the
silica water interface assuming total adsorption): clumps are initially formed at the emulsion/air interface. They are progressively
expelled from the interface, forming a visible ring around the rotating plate of the rheometer. (b) Addition of 1 cmc of CTAB in
the continuous phase. The sample does not exhibit clumping anymore.

in the bulk phase. This phenomenon is reminiscent of

mineral flotation frequently used in the mining industry
to separate valuable minerals from other materials in their
host environment. Minerals are first hydrophobized by
the adsorption of surfactants at low concentration and
separated by attaching themselves to rising air bubbles.12
In our experiments, the silica particles covering the
emulsion drops have been partially hydrophobized by
CTAB and can therefore adhere to the air/water interfaces.
The rigid clumps are progressively expelled out of the
rheometer gap, and the process goes on at the level of the
emulsion/air interface, until almost complete destruction
of the material. The phenomenon is illustrated in Figure
6a. Exceptionally, the emulsion was sheared in parallelplate geometry (instead of Couette geometry) in order to
easily visualize the effect: rigid clumps have been expelled
several centimeters around the rotating plate. Clumping
also occurs if, for example, the emulsions are submitted
to vigorous manual shaking. Coupling between agitation
and permanent extension of the emulsion/air interface
produces irreversible clumping, which again destroys the
emulsions after a sufficient period of time. To avoid this
phenomenon, we modified the wettability of the droplet
surfaces by incorporating CTAB. The emulsions were
fabricated according to the formula defined in section 2.1
(low surfactant content). After cooling, that is, when the
paraffin droplets return to the solid state, surfactant was
added in the continuous phase up to a concentration of 1
cmc. Under such conditions, the shear experiments could
be carried out without the above-described artifact (see
Figure 6b). We checked that the surfactant addition did
not produce any desorption of the solid particles as far as
the droplets remained in the solid state. Indeed, no silica
sediment was observed after allowing the emulsions to
cream for 24 h. Moreover, the emulsions remained stable
for at least 1 month at room temperature, while, as
explained in section 1, emulsions stabilized by surfactant
alone exhibit rapid and irreversible clumping (after some
hours). Therefore, although the particle wettability has
been varied, the emulsion stability is dominated by the
particle layers which remain immobilized or mechanically
trapped at the solid oil/water interface. However, warming
the solid-stabilized emulsions up to 60 C followed by
cooling at T ) 25 C resulted in partial destruction of the
materials. This behavior suggests that, in the presence 1
cmc of CTAB, silica desorption takes place as soon as the
(12) Rosen, M. J. Surfactants and Interfacial Phenomena; Marcel
Dekker: New York, 1989.

Figure 7. Evolution of the viscosity for a paraffin-in-water

emulsion stabilized by P2 particles, sheared at ) 20 Pa. Ds
) 30 m and ) 41.3%. T ) 25 C.

droplets are melted. Desorption is expected at 1 cmc, since

the particle surfaces become hydrophilic.7 If oil is in the
liquid state, the particles recover some mobility and can
leave the interface. The kinetic stability is then dominated
by the adsorption of surfactant, and as stated above, the
emulsion is partially destroyed after only a few hours.
This is why, before shear experiments, we avoided
exposing the emulsions to temperatures higher than 40
C (paraffin melting temperature) once CTAB was added
at 1 cmc.
We measured the evolution of the viscosity, , as a
function of time, at constant stress ) 20 Pa and T ) 25
C. A typical curve is presented in Figure 7. The weak
decrease in viscosity observed at short times can be
attributed to a partial deflocculation of the paraffin
globules. After this initial step, the viscosity exhibits a
slow monotonic increase that most probably reflects the
progressive formation of shear-induced droplet aggregates.
Finally, dramatically increases over at least one decade,
reflecting a sudden gelation/destabilization of the system.
This was confirmed by moving the rotor up: the emulsions
became remarkably rigid. Moreover, they could not be
redispersed when diluted in pure water under agitation,
thus suggesting that the colloidal gel formed under shear
contains partially coalesced droplets. We define the socalled gelation time, , as the time corresponding to the
maximum value measured for the viscosity. The sudden
jump offers a way to measure with sufficient accuracy.
However, it should be noted that the viscosity measure-

Particle-Stabilized Emulsions

Figure 8. Evolution of the gelation time, , as a function of the

droplet fraction for paraffin-in-water emulsions with Ds ) 30
m stabilized by the three types of particles. T ) 25 C. The
lines are only a guide to the eyes. The abrupt decay of the line
indicates that dramatically vanishes above a critical fraction,
* (defined by the intercept with the axis).

ments at longer times were subject to large irreproducible

fluctuations: the system was presumably exhibiting either
fractures or plug flow once gelled (t > ). It is worth
noting that the gelation phenomenon is directly linked to
the crystallizable nature of the droplets. We identically
prepared an oil-in-water emulsion (Ds ) 30 m, ) 35%)
stabilized by P2 particles with a paraffin which is fluid
at room temperature (from Merck, CAS no. 8012-95-1,
density F ) 0.85 gcm-3). Gelation did not occur in the
presence of liquid paraffin droplets, and only a small
increase in viscosity was observed after shearing the
sample for 10 h. The same behavior was obtained for an
emulsion comprised of pure fluid dodecane (Merck, purity
>99%) at T ) 25 C.
In Figure 8, we plot the evolution of as a function of
the paraffin mass fraction for emulsions with an average
diameter of Ds 30 m and the three types of particles.
Although the data are a little bit scattered, they reveal
interesting issues. In the presence of P2 and P3 particles,
the data follow the same qualitative evolution: weakly
depends on for 30% < < 45% and dramatically
decreases above a critical value, * (47 ( 2)%. We could
not measure for samples with a mass fraction lower
than 30% because of the low viscosity of the emulsions:
at the applied stress ( ) 20 Pa), the resulting shear rate
exceeds the upper measurable limit of the apparatus (2500
s-1). For > *, gelation occurred during sample loading,
reflecting the strong shear sensitivity of the most concentrated samples. This is why, in Figure 8, no data are
reported above *. In the presence of P1 particles, the
gelation time exhibits a more regular decrease with and
is shorter than that in the presence of P2 and P3 particles.
This result suggests that P1 particles are less efficient in
stabilizing the solid paraffin globules against flow-induced
gelation/coalescence. Note that P1 particles possess the
smallest primary particle diameter among the three silica
types that were probed in the present study. In Figure 9,
we examine the influence of the droplet average diameter
for P2-stabilized emulsions. Interestingly, the values
measured for the smallest globules (Ds ) 13 m) are much
larger, while the critical mass fraction is smaller, * (33
( 2)%.
3. Discussion. We now comment on the characteristic
features of the gelation process. Davies et al.13 have
explored the shear stability of protein-stabilized emulsions
containing triglyceride crystals. Constant stress experi(13) Davies, E.; Dickinson, E.; Bee, R. Food Hydrocolloids 2000, 14,
145.

Langmuir, Vol. 21, No. 10, 2005 4321

Figure 9. Evolution of the gelation time, , as a function of the

droplet fraction for paraffin-in-water emulsions with variable
droplet diameters stabilized by P2 particles. T ) 25 C. The
lines are only a guide to the eyes.

ments were carried out, and the authors observed a slow

variation regime followed by a rapid increase in the
viscosity, exactly as in our systems. The problem of gelation
in flowing suspensions is one of the fundamental problems
in colloid science and has motivated several theoretical
developments. If we consider the aggregation of dilute
hard spheres, two regimes are usually distinguished. At
the first stages, the process is dominated by doublet
formation and involves collisions between two particles.
At longer times, large clusters appear and each cluster
can grow by the accretion of any other primary particle
or cluster. Potanin14 argues that the evolution of the system
can be correctly described considering that all the particles
are combined into uniform aggregates of identical radius.
In other words, the most probable mechanism of aggregation is of a hierarchical type and involves cluster-cluster
aggregation, thus explaining the fast gelation occurring
at the approach of (see Figure 7). In our case, the process
of gelation can be more complex than the simple picture
proposed for dilute suspensions of undeformable hard
spheres. The paraffin behaves like a soft waxy solid that
may undergo plastic deformations. The adsorbed silica
particles form a rigid bidimensional network which can
also experience plastic deformations during droplet collisions. The flow-induced structures certainly result from
a complex interplay between the attractive colloidal
interactions, the intrinsic plasticity of the droplets and of
the interfaces, and the applied shear. In the following, we
shall only comment on some general tendencies, since a
more profound comprehension of the kinetic evolution of
the emulsion viscosity would require a direct imaging of
the structures formed in the sample during the shearing.
The gelled materials resemble elastic solids and cannot
be redispersed into primary droplets. Therefore, the initial
connected structure has been transformed into a new one
with enhanced rigidity. This is due to the fact that the
emulsions have undergone partial coalescence under the
effect of shear; the enhanced rigidity reflects the formation
of irreversible bridges between the droplets. It can be
argued that some crystals protrude across the adsorbed
particle layers during the solidification process. Another
possible explanation is that the shear-induced forces drive
the droplets together and that the friction experienced by
the rough surfaces progressively induces plastic deformations, allowing the formation of uncovered patches. In the
shear flow, the droplets undergo collisions and partial
coalescence may occur if two uncovered patches are
involved in the contact (Figure 10). Irreversible bridges
can also be formed if a covered area collides with an
(14) Potanin, A. A J. Colloid Interface Sci. 1990, 145, 140.

4322

Langmuir, Vol. 21, No. 10, 2005

Figure 10. Schematic representation of partial coalescence

inducing gelation: (a) general scheme; (b) partial coalescence
between two uncovered patches; (c) irreversible bridging
between a covered patch and an uncovered one.

uncovered patch. The fraction of surface uncovered by the

solid particles is certainly small, so the droplets must
experience many collisions before a coalescence event takes
place or an irreversible bridge forms. This explains the
very long induction times measured for < *. Following
the same scheme, larger silica particles should be more
efficient in protecting the droplets against partial coalescence, since they maintain the oil surfaces apart at larger
distances during collisions, thus lowering the probability
for irreversible bridges (of any kind) to be formed. Such
a tendency is confirmed in Figure 8, where the characteristic gelation times decrease as the stabilizing silica
particles become smaller.
For a given particle type, the average oil droplet
diameter influences both the quiescent and shear stability
of the emulsions: smaller droplets appear to be more
resistant against partial coalescence. We tried to fabricate
emulsions with Ds ) 60 m using P1 particles (7 nm), but
the systems turned out to be completely unstable.
However, we obtained stable emulsions with Ds ) 12 m
using the same particles. The data in Figure 9 correspond
to systems with different average droplet diameters
fabricated in the presence of P2 particles. Below *,
exhibits a non-monotonic evolution with the average
droplet size [(30 m) < (60 m) < (13 m)], certainly
resulting from a complex interplay between hydrodynamic
and crystallization effects, all of them being dependent
on the characteristic droplet size. It is likely that the
diameter of the oil globules influences both the size and
the characteristic shape of the crystals. In the limit of
small droplet diameters (Ds ) 13 m), an increasing
number of silica particles may activate the nucleation
process because of the larger surface-to-volume ratio.
Consequently, more crystals with smaller size are likely
to be formed and protrude through the interface over
smaller characteristic lengths, resulting in a more efficient
stabilization against partial coalescence at low droplet
fraction.
At the applied shear stress ( ) 20 Pa), a sharp transition
occurs at a critical droplet fraction, *: the induction time,
, dramatically falls at the approach of *, and for > *,
the gelation is almost instantaneous. Note that this
phenomenology was observed with solid paraffin and not
with the liquid one, as stated in section 2.4. In the absence

Giermanska-Kahn et al.

Figure 11. Paraffin droplets stabilized by silica particles

(diameter 100 nm) functionalized by hydrophilic (aminopropyl)triethoxysilane groups to an estimated density of 15 chains per
nm2 of silica. T ) 25 C. The surface was hydrophobized by
sodium dedecyl sulfate. The continuous phase is a 2:3 (wt)
mixture of ethanol and water. The presence of ethanol improves
the solvent quality for (aminopropyl)triethoxysilane groups.
Consequently, the solid particles are quite well dispersed in
the continuous phase,17 and the paraffin droplets are not
aggregated.

of shear, we observed a gradual transition of the emulsions

from fluid to solid as the droplet fraction increased. Such
a transition is clearly illustrated in Figure 5 where the
most concentrated sample does not collapse (flow) anymore
under its own weight. Oscillatory rheological measurements were performed with emulsions stabilized by P2
particles and Ds ) 30 m. The emulsions exhibit viscoelastic behavior with the storage, G, and loss ,G, moduli
varying in the range 50-2000 and 10-400 Pa, respectively, as the droplet fraction increases from 30 to 45%.
We only provide orders of magnitude, since the values of
the rheological moduli sensitively depend on the history
of the emulsions, that is, on the concentration procedure
and the loading rate (in the rheometer). The comparatively
large G values reveal the essentially elastic nature of the
materials and the presence of stress bearing paths in the
samples. Above a threshold droplet fraction, *, we
observed that the gels turned into rigid materials made
of irreversibly connected droplets (they could not be totally
redispersed into individual droplets). The value of *
depends on the procedure applied to concentrate the
emulsion, being (54 ( 2)% if water is rapidly sucked by
the capillary method described in section 2.3. The fast
instability occurring in the presence of shear was obtained
at a critical droplet fraction of the same order but slightly
smaller than the previous one: (47 ( 2)% for P2 particles
and Ds ) 30 m. We believe that the two instabilities have
the same origin and that the differences in the critical
droplet fraction only reflect the influence of shear. In the
presence of solidified droplets, as increases, the packing
constraints and the intrinsic roughness of the surfaces
progressively hinder local rearrangements of the droplets.
It can be argued that, in the presence of shear and at a
sufficiently high droplet fraction, frictions between the
surfaces in contact rapidly deform the particle layers,
causing plastic deformations and exposing the droplets to
partial coalescence. The droplet fraction at which this
phenomenon becomes almost instantaneous is obviously
dependent on the mechanical treatment (applied shear)
imposed to the emulsion.
Conclusion
In this paper, we have investigated the efficiency of
colloidal particles in stabilizing solid paraffin droplets.

Particle-Stabilized Emulsions

Monodisperse materials with remarkable kinetic stability

under both quiescent and flow conditions could be
obtained. We could generalize the use of solid particles by
varying the type of particles as well as their surface
properties.15 An example is given in Figure 11. The
stabilizing silica particles were obtained following Stobers
synthesis method.16 Their surface was initially covered
by hydrophilic (aminopropyl)triethoxysilane groups15,17
and was hydrophobized by adsorbing anionic sodium
dodecyl sulfate at a very low concentration. Figure 11
shows an emulsion stabilized by such particles (dp ) 100
nm): surprisingly, the paraffin droplets adopt (on average)
an ellipsoidal shape in the solid state. This example clearly
illustrates a situation where the presence of solid particles
at the interface influences the paraffin solidification, since
(15) Schmitt, V.; Kahn, J.; Reculusa, S.; Ravaine, S.; Arditty; LealCalderon, F. French patent no. 04 00761, Jan 27, 2004 [assigned to
Centre National de la Recherche Scientifique (CNRS)].
(16) Stober, W.; Fink, A.; Bohn, E. J. Colloid Interface Sci. 1968, 26,
62.
(17) Reculusa, S.; Masse, P.; Ravaine, S. J. Colloid Interface Sci.
2004, 279, 471.

Langmuir, Vol. 21, No. 10, 2005 4323

the same emulsion droplets stabilized by surfactant adopt

irregular shapes (like in Figure 1). We could also obtain
kinetically stable emulsions with silica particles hydophobized by n-octyltriethoxysilane.15-18 In this latter
case, the hydrophobizing agent is not adsorbed but
chemically grafted to the surface through a covalent bond.
We hope that the results presented here will widen the
application field of oil-in-water emulsions comprised of
solid droplets [food, pharmacy, cosmetics, road surfacing
(synthetic bitumen emulsions), etc.] and will provide a
useful guidance for the formulation of such materials.
Acknowledgment. The authors are very grateful to
Pr. B. P. Binks for introducing them to solid-stabilized
emulsions. Dr. Reculusa and Prof. Ravaine are acknowledged for providing the functionalized silica particles.
Financial support from Le Conseil Regional dAquitaine
was strongly appreciated.
LA0501177
(18) Reculusa, S.; Ravaine, S. Chem. Mater. 2003, 15, 598.