Rheol Acta

DOI 10.1007/s00397-006-0089-z ORIGINA L CONTRIBUTION

Julien Mougel
Oscar Alvarez
Aging of an unstable w/o gel emulsion
Christophe Baravian
François Caton
with a nonionic surfactant
Philippe Marchal
Marie-José Stébé
Lionel Choplin

Received: 29 June 2005 O. Alvarez . P. Marchal . L. Choplin

Accepted: 6 February 2006
# Springer-Verlag 2006
This work was presented at the congress
AERC 2005 in Grenoble, France.
J. Mougel (*) . C. Baravian . F. Caton
Laboratoire d’énergétique et de
mécanique théorique et appliquée
CNRS UMR 7563,
2 avenue de la Forêt de Haye BP 160,
Vandoeuvre-lès-Nancy,
Cedex 54501, France
e-mail: julien.mougel@ensem.inpl-nancy.fr
Tel.: +33-3-83595710
Génie chimique des milieux
rhéologiquement complexes BP 451,
1 rue Grandville,
Nancy, Cedex 54001, France
M.-J. Stébé
Groupe Physico-Chimie des colloïdes
CNRS UMR 7565,
Université Henri Poincaré BP 239,
Vandoeuvre-lès-Nancy,
Cedex 54506, France
Abstract We study an unstable
highly concentrated emulsion of water
droplets in oil with a nonionic sur-
factant. A technique of light diffusion
coupled to a rheometer allows simul-
taneous measurement of average
droplet radius R and emulsion shear
elastic modulus G0 during time. Over
the studied range of volume fraction
(from 71 to 95%), we show that
Princen and Kiss’ (J Colloid Interface
Sci 112:427–437, 1986) model does
not apply. A dimensional analysis
based on the hypothesis of dominant
van der Waals forces is proposed for
nonionic surfactants, which is in good
agreement with experimental data. We
also show that the measured average
droplet volume increases linearly with
time and that the coalescence rate
strongly depends on the volume frac-
tion in relation with different topolo-
gical conformations of droplets.
Keywords Concentrated emulsion .
Coalescence rate . Nonionic
surfactant . Elastic modulus .
Water-in-oil emulsion

Introduction Another coalescence model is Ostwald ripening, which

Long time stability of concentrated emulsion is a widely
studied and complex field of investigation (e.g., Princen
and Kiss 1986; Bibette et al. 1999; Langevin 1998; Taylor
1995). Indeed, three main mechanisms were shown to lead
to droplet coalescence. Firstly, the Schmoluchowski model
(see, for example, Langevin 1998) is built on the hypoth-
esis that two droplets in contact coalesce. The main
consequence is that the number N of droplets in volume
unit decreases during time leading to a complete phase
separation. This evolution is given by dN =dt /
N 2 and
implies that the droplet radius follows R  t 1=3 :
occurs because of the polydispersity of the system. Small
droplets disappear for the profit of bigger ones because of
the Laplace pressure difference and due to the dispersed
fluid diffusion through the continuous phase (Langevin
1998). The speed of this mechanism depends on the
diffusion coefficient of the dispersed phase in the other and
the interfacial tension γ (see Taylor 1995; Walstra 1996)
also leading to an evolution of R with t1=3 :
For emulsions with a concentration that is higher than
the close packing fraction, droplets are highly deformed
and separated by a thin film of continuous phase (like in
foams). The coalescence happens when this film breaks up.
This complex mechanism involves, for emulsions, the
stability of the interface between oily and aqueous phases
(see Bibette et al. 1999; Langevin 1998). Thermal agitation
can create fluctuations of the film thickness and amplitude
increases when droplets get closer. The fluctuations of
concentration in the layer of surfactant are another source
of instability.
In parallel to the modeling complexity, experimental
studies are difficult due to the nonstability of the system
and its opacity to visible light. Indeed, because of the
turbidity of concentrated suspensions, direct microscopy or
small angle light scattering techniques cannot be used
easily. Moreover, in many cases, the samples are unstable
with respect to dilution or can simply not be diluted in
water [e.g., water-in-oil (w/o) emulsions or foams]. In
contrast, multiple light scattering systems, such as steady
light transport (Baravian et al. 2004) or dynamic light
scattering (Brown 1993), are well suited for concentrated
and opaque suspensions.
Most experimental studies on emulsion stability uses
ionic surfactants, making electrostatic repulsion forces
dominant. In this case, the heuristic relation proposed by
Princen and Kiss (1986) is verified (e.g., Princen and Kiss
1986; Ravey et al. 1998; Taylor 1996) or slightly modified
(Mason 1999; Bressy et al. 2003). To our knowledge, only
Pal (1999) performed droplet size and elastic modulus G0
measurements on a nonionic emulsion.1 On his figure 9, we
see that the variation of experimental G0 R=γ with the
volume fraction is not well described by Princen and Kiss’
model. In the case of a nonionic surfactant, because there is
no electrostatic charge on the surface of droplets, the
dominant behavior of the system could be due to van der
Waals forces (see Bibette et al. 1999). A natural question
arising from these observations is whether the nonionic or
ionic characteristic of the surfactant does fundamentally
change the properties of the emulsion.
To explore this possibility, we study a gel emulsion with
a nonionic surfactant different from that of Pal (1999). For
various concentrations in dispersed phase, we follow the
temporal evolution of droplet radius and sample shear
elastic modulus. In the first part of this work, we describe
the chemical composition of the samples, the preparation
process, and briefly the measurement method. The second
part deals with the coalescence mechanism and finally, a
new dependence of the elastic modulus with the average
droplet size and the volume fraction is proposed on the
hypothesis of dominant van der Waals forces.
Materials and method
Water was deionized and milli-Q filtrated with a Millipore
apparatus. The oil is a Dodecane obtained from Labosi
1 The following occurrences of “nonionic (ionic) emulsion” will be
denoted by an emulsion in which the surfactant is nonionic (ionic).
(99% Purum) and the surfactant, dispersed in oil, is a
sorbitan monooleate [Span80, hydrophile-lipophile bal-
ance (HLB)=4.3] purchased from Aldrich. The refractive
indices of water and oil phase are 1.33 and 1.443,
respectively. The composition of the samples in mass
fraction is between 74 and 96% for the aqueous phase and
the surfactant/oil weight ratio is 0.81 to keep the same
surface tension γ ¼ 2:8 mN/m for all samples. Indeed, the
surfactant concentration is, under this condition, greater
than the critical micellar concentration for all the samples
where the volume fractions in dispersed phase are 71, 73,
75, 78, 85, 90, 92, 93.5, and 95%. The total quantity of
each sample prepared is 84.1 g.
The emulsions are prepared at 27 C by incorporation of
the aqueous phase into the oil phase containing the
surfactant (semi-batch system). The emulsification process
was divided in three steps: (1) dispersion of Span80 in oil
and homogenization (10 min at 500 rpm), (2) aqueous
phase incorporation at a flow rate of 4 g/min and an
agitation speed of 500 rpm, and (3) homogenization of the
emulsion during 5 min at the same agitation speed. The
agitation system used was a Turbo test 33/750 P (Rayneri
Groupe VMI) equipped with a speed control to ensure a
constant stirring rate independent on the evolution of the
emulsion viscosity. Our samples are prepared with a 45
pitched-blade turbine of 50 mm diameter in a cylindrical
glass tank (70 mm diameter). The turbine is positioned on
the free surface of the oil phase before aqueous phase
incorporation (see, e.g., Shervin et al. 1991).
The measurement device is a steady light transport
apparatus (see Baravian et al. 2004, 2005) placed on an
AR1000 rheometer from TA Instrument. This apparatus
allows simultaneous light transport length l  and
rheological measurements. Each experiment begins
roughly 2 h after the end of the preparation process and
lasts for about 64 h.
The transport length l  is related to Mie theory through
φl ¼ ð43 πR3 Þ=½Csca ðx; mÞð1
gðx; mÞÞ where x ¼ kR

with k as the wave number and m as the ratio of the
particle to medium refractive indices. Csca and g are the
scattering cross-section and the anisotropy factor, respec-
tively. Knowing the optical properties of the emulsion
phases and the volume fraction φ of droplets, Mie theory
directly relates the transport length to the average radius
of droplets. Under our experimental conditions
(m ’ 0:92; 100 < φl  < 700 μ m), the average droplet
radius R (in μ m) shows a linear dependence with φl 
(in μ m).2 This dependence is well described by R ¼ α
φl
β where α ¼ 0:038 and β ¼ 0:766 μ m are the best-
fit parameters using a standard least square method.
2 Although our samples are highly concentrated, dependent diffusion
is not involved because the average distance between droplets center
is always big enough compared to the laser wavelength (Tsang et al.
2000).
 Rheological test consists of the application of oscillation 100
0.01 0.1 1

stress of 1 Pa at a frequency of 1 Hz to the sample, which is 1−φ

30
much smaller than the droplet coalescence rate. As shown
on Fig. 1, G0 decreases with time and increases with re- 10

R0 (µm)
95%
spect to the volume fraction. We follow the temporal
evolution of two properties of the emulsion: the elastic 1

R (µm)
20
modulus and the average radius of droplets. 93.5%

92%

Coalescence
We present on Fig. 2 the results obtained with the steady
light transport apparatus. First, we observe that the average
size of droplets increases during time. Two tests were done
at a volume fraction of 95%, showing an excellent
reproducibility (see Fig. 2). To verify that the measured
size evolution is significant, a stabilized emulsion at φ ¼
93:5% was prepared by adding NaCl (about 2.5% weight
of the aqueous phase). Compared to the nonstabilized one,
the evolution of the stabilized emulsion is negligible. We
also notice that whatever the volume fraction, the same
agitation rate is used during the preparation process so that
the first measured radius R0 is different for each sample.
The graphic in the insert of Fig. 2 shows that the variation
of R0 with the volume fraction φ of water droplets is
proportional to 1=ð1
φÞ with a factor of 0:795μ m in the
whole range of volume fraction. We verified that every-
thing else being equal, a different R0 (obtained by
changing the agitation rate) does not significantly change
the kinetics.
For all samples (from φ ¼ 0:71 to 0.95), we verify that
the average radius follows a t 1=3 evolution law:
RðtÞ ¼ ½R30 þ ω  ðt
t0 Þ1=3;
1000
95%
800 93.5%
10
93.5% (stabilized)
71%
0
1 10 100
t-t0 (hours)
Fig. 2 Time evolution of average particle radius R for various
volume fractions.  Experimental points, solid lines are the best fits of
Eq. 1. þ Stabilized emulsion at 93.5% in volume fraction. Insert: 
initial radius as a function of volume fraction
, solid line
0:795=ð1

Þ. For clarity reason, not all the data are plotted
where ω is the coalescence rate, R0 and t0 correspond to
the first measurement. A standard least square adjustment
of Eq. 1 to experimental curves (see Fig. 2) allows the
determination of ω for each sample. This coalescence rate
is known, for a given volume fraction, to be strongly
dependent on the HLB (Aronson and Petko 1993). Figure 3
shows that ω increases with the volume fraction until
φ1 ’ 0:75, then remains constant until φ2 ’ 0:90 , and
finally increases again. φ1 and φ2 could be related to the
(1) clustering of droplets from the close maximum packing
fraction without significant deformation to a polyhedral
shape when φ2 is reached.
0.1

92%
600
85%
G’ (Pa)

0.01
ω (µm3/s)

78%
400

0.001
200

0
1 10 100 0.0001
t-t0 (hours) 0.7 0.8 0.9 1
Volume fraction φ
Fig. 1 Evolution of the samples elastic modulus G0 at various
volume fractions. For clarity reason, not all the data are plotted Fig. 3 Variation of the coalescence rate ! with the volume fraction
Fig. 4 G0 vs R. Except for the 7
sample at 73% in volume
fraction, the basic plot of the Slope -2
data shows that, in our case,
G0 is correlated with 1=R2 6.5 92%

85%

Ln G’ (Pa)
6
75% 95%

5.5
90%
73% 93.5%

5
78%
Slope -1
4.5
1 1.5 2 2.5 3 3.5
Ln R (µm)

Elastic modulus than 75%, corresponding to the first transition regime in

Fig. 3. Another experimental observation is the divergence
Figure 4 shows the elastic modulus (G0 ) dependence with of G0 R2 when φ approaches 1 (Fig. 5). This divergence is,
the average droplet radius R for different volume fractions. again, not taken into account in Princen’s model.
This figure is obtained from Figs. 1 and 2. It is clear that the From dimensional considerations, we can express the
well-known Princen and Kiss (1986) model does not apply elasticity as follows
to our experimental data because G0 does not vary like 1=R
(the corresponding slope
1 is plotted on Fig. 4). Indeed, W
G0  (2)
we find that G0 is better correlated to 1=R2 (see slope
2 V
on Figs. 4 and 5), especially for volume fractions greater
where W has the dimension of an energy and V the
100
dimension of a volume. To take into account the divergence
Present work of G0, we must consider V as the continuous phase volume
Pal’s experiments by unit droplet Vf :
φ /(φc − φ )
1
φ
· Princen for the present work Vf / R3 : (3)
2
Princen for Pal φ
G' R
10
2π AD0γ The energy W therefore has to be proportional to R to
describe the correlation of G0 with 1=R2.
In a general point of view, elasticity of concentrated
dispersions was closely related to the pair interaction
potential energy (e.g., Quemada and Berli 2002). On the
other hand, in the case of emulsions concentrated above the
1
0.7 0.8 0.9 1
critical random packing volume fraction, the elasticity is
related to the interfacial energy of deformed droplets
Volume fraction φ (Princen and Kiss 1986). Nevertheless, this local elasticity
Fig. 5 G0 R2 =ð2AD0 Þ vs
. We compare our results () and Pal’s is transmitted at the sample scale through the interaction
experimental data () to the model of Eq. 7 (solid line). The value potential between droplets (electrostatic repulsion in all
of the parameters are A ¼ 3:66 and
c ¼ 0:96. For Pal’s work, we cases where Princen model is verified). In the following,
take R ¼ 1:675 m (R½4; 3 from the size distribution) and  ¼ we propose to explore the possibility that the dominant
0:77 mN/m. The dashed-dotted and dashed lines represent
Princen’s model for the present work at t ¼ 2 h and for Pal, interaction energy W is due to van der Waals forces in the
respectively case of nonionic surfactant.
 Amplitude of van der Waals energy between two
identical droplets in a different surrounding medium can
be expressed as (Israelachvili 1991):
AH R
W ¼ ; (4)
12D
where D is the distance between the surfaces of the two
droplets and AH ¼ 24πγD20 is the Hamaker constant with
D0 the intermolecular distance. In our case, as the droplets
are in contact, we assume that D does not depend on the
volume fraction and is of the order of the intermolecular
distance, i.e., D  D0 . Therefore we write
W ¼ 2πγD0 R:
Equations 2, 3, and 5 lead to the following expression
for G0:
2πγD0 φ
G0 / : (6)
R2 ð1
φÞ
We see that this approach leads to a divergence at φ ¼ 1.
However, a better empirical relation in comparison with
experiments is
2πγAD0 φ
G0 ¼ ; (7)
R2 ðφc
φÞ
where A is the proportionality coefficient. The critical
volume fraction φc might account for the droplet surface
curvature and very short-range interactions. This model
is valid for a wide range of volume fractions and droplet
sizes, as shown on Fig. 5 on which all experimental
points of Fig. 4 are drawn. The best fit to our
experimental data provides the following values: A ¼ 3:
66 and φc ’ 0:96 , taking D0 ¼ 30 nm (Dukhin and
Goetz 2004) as the micelle diameter.
The square symbols on the Fig. 5 shows the experi-
mental data of Pal (1999). With the same φc , the same
value of A and D0 ¼ 6 nm (Molina-Bolivar et al. 2002),
Pal’s data superimposes on the present work results without
any adjustment parameters, although a different nonionic
surfactant (Triton X-100, HLB=13.5, γ ¼ 0:77 mN/m)
was used in an oil-in-water (o/w) emulsion.
Conclusion
(5)
The steady light transport technique allows the simulta-
neous measurement of the temporal evolution of the
sample shear elastic modulus G0 and droplet average radius
R for samples at various volume fractions φ.
We find that the coalescence law R  t 1=3 applies in our
system for the whole range of volume fractions. The
coalescence rate shows different domains in relation with
the clustering of droplets.
The relation that we found between G0, R, and φ (Eq. 7)
differs from Princen and Kiss’ (1986) model, probably due
to the use of a nonionic surfactant (Span80) in the
preparation of our samples. Based on dominant van der
Waals interactions, a tentative model is built up. This model
also describes other results obtained with another nonionic
surfactant for an o/w emulsion (Pal 1999).
Further investigations with other nonionic surfactants
have to be performed to verify if this behavior is only valid
in some particular cases or if it is a more general one.
Acknowledgement We thank Daniel Quemada for useful remarks
and comments.

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