Colloids and Surfaces A: Physicochem. Eng.

Aspects 461 (2014) 336343

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

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

Production of W/O/W double emulsions. Part I: Visual observation of

deformation and breakup of double emulsion drops and coalescence
of the inner droplets
Anna Schuch a, , L. Gary Leal b , Heike P. Schuchmann a
a
b

Institute of Process Engineering in Life Science, Section I: Food Process Engineering, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany
Department of Chemical Engineering, University of California at Santa Barbara, Santa Barbara, CA 93106, USA

h i g h l i g h t s

g r a p h i c a l

a b s t r a c t

Deformation and breakup of double emulsion drops not inuenced by

inner dispersed phase content.
The oilwater interface is immobilized by the surfactant PGPR.
Coalescence of inner droplets is only
observable with a hydrophilic surfactant.
Coalescence in non-deformed as well
as in deformed double emulsion
drops.

a r t i c l e

i n f o

Article history:
Received 10 October 2013
Received in revised form
20 November 2013
Accepted 21 November 2013
Available online 1 December 2013
Keywords:
Double emulsion
Drop breakup
Filled droplet deformation
Coalescence
Immobilized interface
Stability

a b s t r a c t
We investigate deformation and breakup of double emulsion drops, in a system consisting of an aqueous
continuous phase and double emulsion oil drops containing smaller droplets of water. The system is stabilized by the presence of the surfactant polyglycerol polyricinoleate (PGPR). Extensional ow generated
in a 4-roll mill is used for these investigations. Steady state deformation is not inuenced by the concentration of the innermost water droplets, and thus, in the range of strain rates studied, is not affected by
the rheological properties of the drop phase. Moreover, drop shapes and relaxation behavior also do not
depend on the disperse phase concentration of the water droplets. Finally, the critical Capillary number
for drop breakup is independent of viscosity ratio. These observations seem to be at least partly the result
of immobilized drop interfaces under the ow conditions that were studied.
An important phenomenon is loss of the innermost water droplets by coalescence with the outer
water phase. This is only observed in this system if a hydrophilic surfactant is dissolved in the continuous
phase. Moreover, if coalescence occurs, coalescence phenomena are observed to be independent of the
deformation and breakup of the double emulsion drop. Coalescence phenomena do not only take place
within seconds but can be observed over several minutes. This implies that instabilities in multiple
emulsions are not mainly governed by process conditions, but are rather an intrinsic consequence of the
formulation.
2013 Elsevier B.V. All rights reserved.

1. Introduction
Abbreviations: fps, frames per second; cmc, critical micelle concentration;
PGPR, polyglycerol polyricinoleate; rpm, revolutions per minute; W/O, water-in-oil;
W/O/W, water-in-oil-in-water.
Corresponding author at: Haid-und-Neu Strae 9, 76131 Karlsruhe, Germany.
Tel.: +49 721 608 43785; fax: +49 721 608 45967.
E-mail addresses: Anna.Schuch@kit.edu (A. Schuch), lgl20@engineering.ucsb.edu
(L.G. Leal), Heike.Schuchmann@kit.edu (H.P. Schuchmann).
0927-7757/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.11.043

Multiple water-in-oil-in-water (W/O/W) emulsions are complex multiphase systems that consist of a water-in-oil (W/O)
emulsion dispersed as drops in a second continuous water phase.
They are also called emulsions of emulsions. The production of
multiple W/O/W emulsions is interesting for different applications
ranging from separation technology [1], encapsulation of sensitive

A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 336343

Nomenclature
Symbols
B
Ca
Cacrit
D
Ds
1
G
h
c
d
L

r

t
t
trelax

breadth of the drop [m]

Capillary number
critical Capillary number
deformation
maximum deformation
inner dispersed phase concentration
strain rate [s1 ]
gap width [m]
continuous phase viscosity [Pa s]
dispersed phase viscosity [Pa s]
length of the drop [m]
viscosity ratio
drop radius [m]
interfacial tension [N m1 ]
time [s]
observation time [s]
dimensionless relaxation time

molecules for food [2,3], cosmetic, agro and ne chemical as well

as pharmaceutical products [46] to fat reduction in food [7].
In order to control the structure of double emulsions, a two-step
emulsication process is mostly used. First, a so called inner W/O
emulsion is produced which in turn is used as the dispersed phase
of the nal W/O/W double emulsion. That means that oil drops
containing smaller inner water droplets have to be broken up in the
second emulsication step. The rheological behavior of an emulsion
depends amongst other properties on its dispersed phase concentration. While showing Newtonian behavior at low dispersed phase
concentrations, the ow of emulsions with high dispersed phase
concentration is known to show non-Newtonian behavior. Effects
like shear thinning and viscoelasticity have to be considered when
investigating the breakup of double emulsion drops.
At low dispersed phase concentrations and at low shear rates,
drops in an emulsion behave as solid spheres. Therefore, the
rheological behavior of such emulsions can be compared to the
behavior of suspensions. The relationship established by Krieger
and Dougherty [8] can be applied to express the viscosity dependence of emulsions on their dispersed phase concentration. For
higher dispersed phase concentrations, shear thinning behavior
can often be observed [9]. This is the result of a rearrangement
of droplets in the uid in order to minimize friction. Elastic behavior can also be observed when the shear rates are high enough to
deform the droplets or when the dispersed phase concentration
of an emulsion is increased till droplets are jammed together and
cannot ow freely anymore [10].
Non-Newtonian behavior of the drop phase, especially elasticity, has been shown to inuence drop deformation and breakup.
Elastic drops are reported to show blunted ends during deformation
compared to the ellipsoidal shapes of deformed Newtonian drops
[11]. Moreover, drop relaxation upon cessation of shear is slowed
down for elastic drops [11,12]. Furthermore, at a given viscosity,
the time required for deformation (i.e. the strain experienced) of
elastic drops is higher than that of drops with Newtonian ow
behavior. This makes breakup of such drops in typical emulsication devices more difcult [13]. As double emulsion drops can show
elastic properties dependent on the inner dispersed phase concentration 1 , it is to be expected that deformation and breakup of
these drops also depends on 1 .
Stroeve and Varanasi investigated breakup of double emulsion
drops visually. They observed the same breakup mechanisms as
described for Newtonian systems [14,15]. Moreover, they found

337

a comparable dependency of critical Capillary number on viscosity ratio as for Newtonian systems [16]. The only difference they
noted in comparison to results for Newtonian drops was a shift of
the typical Grace curve toward higher viscosity ratios. This investigation focused on drop breakup. However, drop deformation was
not investigated.
As inner water droplets in double emulsions have to be stabilized against coalescence with each other, surfactants are used
in the oil phase. Different investigations show that a surfactant
can immobilize the interface during drop deformation and thus
inuence drop deformation and breakup [1719]. The surfactant molecules on the interface can be transported toward the
drop ends by the ow of the continuous phase. This transport
leads to differences in surfactant concentration between drop ends
and the middle of the drop. Therefore, Marangoni stresses are
induced which work against the ow of the continuous phase
the interface is immobilized [20]. Whether the interface is immobilized or not can theoretically be estimated by calculating the
Marangoni number. It is dened as the ratio of distorting viscous stresses to restoring Marangoni stresses. Therefore, it is
inuenced by the applied viscous stresses as well as by the adsorption and surface active properties of the surfactant used [19]. It
is further shown that immobilized interfaces lead to critical Ca
numbers for drop breakup that are independent of viscosity ratio
for viscosity ratios  < 0.1 [21]. Another effect correlated to the
presence of surfactant at the interface of a drop is tip streaming. Tip streaming is a drop breakup phenomenon that occurs
at ow rates below the critical ow rate for deformation and
breakup of the whole drop. Small daughter drops are ejected
from the thin threads formed at the ends of a deformed drop
[22,23].
An important phenomenon inuencing double emulsion stability and thus functionality is coalescence of the inner water droplets
with the outer water phase. The occurrence of this mechanism is
described in several works [2427]. From newly formed double
emulsion drops no longer being fully packed, Stroeve et al. concluded that the inner water droplets must get lost during breakup
and formation of the outer drop. They presumed that the coalescence process causing this loss has to occur in the nodal regions
during thinning and breaking of the double emulsion drops [15].
Another work indicating a connection between drop breakup and
this coalescence process was carried out by Muguet et al. [28].
They observed a correlation between release of the inner water
droplets and the Capillary number applied during breakup. Results
of our own work indicate that release of water in W/O/W emulsions due to this coalescence process is correlated to the drop size
of the oil drops [29]. Another attempt to describe the mechanism
of coalescence in double emulsions is based on circulation of the
inner droplets caused by external ow around a double emulsion drop [30]. But in none of these works was coalescence of
the inner droplets with the outer phase visually observed. In the
present work we want to visualize coalescence in W/O/W drops at
rest as well as during deformation and breakup. The knowledge of
when and where coalescence occurs can help to understand this
coalescence process and develop a model describing the mechanism.
Therefore, the present work aims to investigate whether the
inner dispersed phase concentration and the resulting rheological
properties of the drop phase inuence deformation and breakup
of W/O/W double emulsion drops. In order to create steady extensional ow, a four-roll mill apparatus was used. This device has
previously been used very successfully for this kind of investigation. Immobilization of the interface by the surfactant was observed
during the experiments. Steady deformation as well as relaxation
of drops with different 1 are observed and shapes of the deformed
drops are analyzed. In addition, breakup of double emulsion drops

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A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 336343

viscosity [Pas]

0,1
0,2

0,3

0,4

0,5

0,6

dispersed phase concentration 1 [-]

Fig. 1. Viscosity  of the inner W/O emulsion at a shear rate of 1 s1 dependent on
its dispersed phase concentration 1 .

is investigated. These experiments enabled investigation of the

inuence of immobilized interfaces and rheological properties of
the dispersed phase.
In order to gain an idea of the general mechanisms of coalescence in double emulsions, videos and pictures of double emulsion
drops were recorded. Several surfactants were used in the outer
phase, while the W/O emulsion drops contained PGPR. These experiments enabled visualization of the coalescence phenomena of
inner droplets with the outer phase. The ndings of this work will
help to understand and describe this coalescence process in double
emulsions and to develop strategies to stabilize lled drop structures in double emulsions.

2. Materials and methods

2.1. Preparation of W/O emulsions
For the preparation of the water-in-oil (W/O) emulsions (inner
emulsion) the surfactant polyglycerol polyricinoleate (PGPR 4175,
Palsgaard, Denmark) was dissolved in canola oil (Floreal Haagen,
Germany) by stirring with a propeller stirrer. The amount of surfactant was 5 wt% relative to the amount of oil, which ensures
total coverage of the interface for the highest concentrations of
the dispersed phase water droplets. After dissolving the surfactant, the dispersed water phase was added and stirred until a
homogeneous emulsion premix was obtained (x50,3 10 m). The
dispersed phase consisted of demineralized water, with 3% NaCl
(Carl Roth GmbH & Co., Germany) used to balance the Laplace pressure by raising the osmotic pressure in the inner droplets of the
double emulsion [31,32]. The W/O/W emulsions were produced
with a dispersed phase concentration of 1 = 0.6. Approximately
300 g of this premix were then further homogenized using the
lab scale colloid mill IKA magicLAB module MK (IKA Staufen,
Germany). The gap width was set to 0.32 mm and a rotational speed
of 10,000 rpm was applied for 2 min in a semi-continuous process. The resulting W/O/W emulsion was then diluted in order to
obtain different dispersed phase concentrations by adding different
amounts of continuous phase (oil + PGPR) and stirring with a propeller stirrer at 200 rpm. The droplet size distribution of the inner
water droplets was measured before and after the dilution in order
to assure that it remained constant. The droplet size distribution of
the inner emulsions can be found elsewhere [29]. The viscosities of
the inner emulsions with different dispersed phase concentrations
measured at a shear rate of 1 s1 are shown in Fig. 1.

Increasing dispersed phase concentration leads to increasing

viscosities. For emulsions with highly dispersed phase concentration (1 = 0.5 and 0.6) elastic properties were detectable in
oscillatory measurements. The results of these measurements can
be found in our earlier publication [29]. The resulting viscosity
ratio  (d /c ) between inner emulsion d and continuous phase
c was in the range of 0.0080.023 dependent on the dispersed
phase concentration of the inner emulsion.
In order to enable visual observation of coalescence of the
inner drops with the outer water phase, another W/O emulsion
with larger inner droplets was produced. The composition of this
emulsion was the same as described previously. It was produced
by adding 35% of the inner water phase (water + NaCl) to the oil
phase (vegetable oil + PGPR) while stirring with a magnetic stirrer.
After adding the water phase, the emulsion was further stirred for
another 60 s. The size of the inner water drops was around 5 m.
2.2. Deformation and breakup experiments
All investigations were conducted in the miniaturized four-roll
mill developed by Hu et al. [33]. It is a smaller version of the original device designed by Bentley and Leal [34]. The cell has a size
of 60 mm 60 mm and a depth of 58.5 mm and is lled with the
continuous uid phase. Four rollers with a radius of 7.2 mm are
centered on an 18.3 mm square which provides a roller gap width
of 3.86 mm and a ratio of roller spacing to roller radius of 1.27. By
controlling the rotation speeds of the rollers, the ow type as well
as the strain rate can be controlled. In the present work, purely
extensional (hyperbolic) ow was applied to deform the droplets.
The double emulsion W/O drops were introduced into the continuous phase by injection using a syringe. The size of these drops
was around 300 m for most experiments. For investigating the
effect of the drop size ratio between the inner water drops and the
outer drop, smaller W/O droplets were introduced into the cell. The
continuous uid phase consisted of light corn syrup (Karo, USA).
The viscosity of this uid was increased to c = 9.6 Pa s by evaporation at room temperature as described elsewhere [15]. This high
viscosity is needed in order to slow down creaming of the droplets
and to enable higher strain stresses. Pendant drop measurements
between W/O drops and corn syrup gave interfacial tensions of
 = 5 0.3 mN m1 independent of the dispersed phase concentration of the W/O drops.
One drop was centered at the stagnation point of the ow by
controlling the four rollers prior to the experiment. This enables
the observation of the drop during the whole transient deformation
experiment. A CCD video camera (Sony XC 75) combined with a
6x zoom lens (ZOOM 6000, Navitar) was used to observe the drop
from below the cell during deformation and breakup. Pictures or
videos (15 fps) of the drop are saved on a computer and analyzed
by extracting the drop contour and measuring the maximum length
L and breadth B. The so-called Taylor deformation parameter D of
the drop is calculated as follows Eq. (1):
D=

LB
L+B

(1)

Moreover, the Capillary number Ca for a drop of radius r at a strain

rate G is calculated using the viscosity of the continuous phase c
and the interfacial tension  (Eq. (2)):
Ca =

c G r


(2)

For a surfactant free drop in linear extensional ow at low Ca numbers (Ca  1) the deformation D is a linear function of Ca and can be
expressed according to Taylors small deformation theory [10]. The

A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 336343

factor describing this proportionality is called the Taylor prefactor

Eq. (3):
D=

19 + 16
Ca
8( + 1)

(3)

In relaxation experiments drops were deformed to an equilibrium

deformation of D = 0.2. Afterwards, the ow was stopped and relaxation back to a spherical shape was observed. The dimensionless
relaxation time trelax was calculated from the actual time t (Eq. (4))
[35]:
trelax =

t
r c

(4)

For the experiments involving coalescence of the inner drops with

the outer continuous corn syrup phase, the following surfactants
were dissolved in the corn syrup: Tween 20, Tween 80 (both Roth,
Germany), Lutensol AT80 (BASF, Germany) and egg yolk powder
(Sanovo, Germany). The concentration of the surfactants was cmc
for Tween and Lutensol and 0.5 wt% for the egg yolk, respectively.
In the latter case, a cmc value is difcult to dene as egg yolk is a
mixture of many interfacially active components. Some of these
components are insoluble in water and thus make the solution
opaque. The 0.5% of egg yolk was found to be a good concentration for the experiments as it still enabled visual observation of the
drop.
3. Results and discussion
3.1. Deformation and breakup of double emulsion (W/O) drops
First of all, the simple observation of big double emulsion
drops with low inner dispersed phase concentration gives important qualitative results about their deformation behavior. A video
sequence of a deformed drop can be found in Section 3.2. The inner
water droplets, which can be seen as tracers in the oil drops, do
not move within the deformed oil drop, as long as it is deformed
at steady state. In clean drops, the ow of the continuous phase
deforming the drop induces a ow inside the drop [36]. A movement of inner droplets would have been expected in that case. In
addition, increasing the stress to the critical Ca number leads to
drop breakup by tip streaming. Binary breakup is only observed
for Ca numbers higher than Cacrit . Both of these observations are
indications for the surfactant immobilizing the interface and thus
inuencing drop deformation and breakup [22]. They are observable for all investigated double emulsion drops, independent of the
presence of a hydrophilic surfactant and its nature.

339

Most of the mathematical investigations as well as experimental investigations concerning surfactant effects consider insoluble
surfactants. Nevertheless, the soluble surfactant (PGPR) used in
our experiments shows the same inuence as described for insoluble ones. According to Eggleton and Stebe this observation can
be explained by a slow adsorption behavior of the surfactant. The
surfactant molecules on the interface are transported to the tips
of the deformed drop as described for insoluble surfactants. As the
adsorption process of new surfactant molecules is not fast enough,
this results in a concentration difference of surfactant molecules
in the interface and this in turn leads to Marangoni stresses
that immobilize the interface [18]. Our observation suggests that
although being a predominantly W/O stabilizing emulsier, PGPR
is also able to immobilize the interface of O/W drops meaning
that it adsorbs noticeably at the O/W interface in mixed systems.
Moreover, the adsorption kinetics of PGPR are not fast enough to
remobilize the interface.
In order to estimate the inuence of dispersed phase viscosity on
steady state drop deformation we calculated the Taylor prefactors
[10]. The Taylor prefactor gives the slope of the curve representing deformation D dependent on Capillary number Ca at low Ca.
Using the viscosity of the W/O emulsion drop and one of the continuous phases, viscosity ratios  between 0.008 at 1 = 0.2, and
0.023 at 1 = 0.6 are calculated. Using Eq. (3) the Taylor prefactors are calculated to be 2.003 for  = 0.008 and 2.008 for  = 0.023.
These expected differences are below resolution of the measurement technique. Therefore, steady state deformations cannot give
any information about viscosity effects on drop deformation. Moreover, it was shown by other researchers that elasticity does not
inuence the slope of the deformation curve [11,37]. That means
that steady state deformations are not expected to be inuenced by
the rheological properties of the dispersed phase. The results conrming this expectation can be found in supplementary material.
Supplementary material related to this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.colsurfa.
2013.11.043.
In addition, the inuence of droplet size ratio between inner
water droplets and outer oil drop was investigated by changing
the oil drop size (results not shown here). These observations also
showed the same dependency of deformation on Capillary number.
No inuence of droplet size ratio between the inner water droplets
and the outer oil drop was observable for Capillary numbers in the
range of 0.050.23.
To further analyze the inuence of rheological properties on the
deformation behavior, drop shapes of the double emulsion drops at
a deformation D equal to 0.2 are considered. Fig. 2 shows exemplarily such drops and the contours extracted from the pictures. Distinct

Fig. 2. Drop shapes (contour left and pictures right) of deformed double emulsion drops at a xed deformation D = 0.2.

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A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 336343

critical Capillary number Cacrit [-]

0,6

ratio of actual to maximum deformation D/Ds [-]

0,7

Cacrit in extensional flow

Grace, 1982/Newtonian system
present work/double emulsions

0,5
0,4
0,3
0,2

dispersed phase concentration

of inner emulsion 1
0.35
0.5
0.6

0,1

0,1
0,0
1E-3

0,01

0,1

viscosity ratio [-]

Fig. 3. Critical Capillary numbers for drop breakup in hyperbolic ow dependent on
viscosity ratio, comparison of own results with results from Grace [38].

inner water droplets are not observable inside the oil drops as their
size is around 0.3 m and thus too small for visual observation.
The drop shapes of double emulsion drops with dispersed phase
concentrations of 0.6 and 0.35 are identical considering the resolution of the camera. The drops do not show blunted ends as
observed by Hsu and Leal [11]. This was also observed for all other
drops of various dispersed phase concentrations. The blunted ends
of deformed elastic drops are known to be a result of internal recirculation in the drops [37]. If the interface is immobilized, as it is
observed in our system, there is no circulation in the drop. Therefore, there is no reason for the occurrence of blunted ends, even if
elasticity of the drops is high enough.
By further increasing the applied strain rate we investigated
breakup of the double emulsion drops. Fig. 3 shows the critical
Ca numbers for drop breakup dependent on the viscosity ratio
(standard deviations are calculated from three experiments). The
viscosity ratios result from different inner dispersed phase concentrations and thus dispersed phase viscosities. They were calculated
using the measured values (see Fig. 1). The continuous phase was
not changed during the experiments. For better comparison, Fig. 3
also shows results from Grace for drop breakup in hyperbolic ow
[16].
Our results show constant critical Ca numbers. This means that
Cacrit is independent of the viscosity ratio and thus also of the dispersed phase concentration of the inner emulsion. In contrast, the
results of Grace for Newtonian drops show increasing critical Ca
numbers with decreasing viscosity ratio in the range between 0.001
and 1. The difference in rheological behavior of the dispersed phase
cannot account for this difference because double emulsion drops
with low inner dispersed phase concentrations also show Newtonian behavior as already shown by us for the exact same emulsion
[29]. The important difference between our investigations and the
ones by Grace is the use of surfactant. While Graces system was
entirely surfactant-free, our system contained PGPR in the oil phase
which immobilized the interface as described above. Our nding
that the critical Ca numbers for drop breakup are independent of
viscosity ratio are in good agreement with numerical investigations
from Bazhlekov et al. for breakup of surfactant covered drops [21].
They found constant critical Ca numbers for viscosity ratios  < 0.1
if enough surfactant was present in the system. Our experimental
results conrm these calculations.
Comparing our results for breakup of double emulsion drops
to those of Stroeve and Varanasi the most prominent difference is
that they observed a strong dependency of Cacrit on viscosity ratio
[15]. They did not observe any indication that the applied surfactant

dimensionless relaxation time trelax [-]

Fig. 4. Drop relaxation (actual to maximum deformation D/Ds over dimensionless
relaxation time t /trelax ) for double emulsion drops with different inner dispersed
phase concentrations 1 .

inuences the drop breakup results although they also used one in
order to stabilize inner water droplets. According to the Marangoni
number, these differences can result from the properties of the different surfactants used or from the applied viscous stresses. As Span
80, which was used in Stroeves work, and PGPR show comparable
adsorption properties [39], an inuence of the surfactant is not to
be expected. Consequently, the difference probably results from the
differing experimental procedures. We slowly increase strain rate
during the observation of one double emulsion drop while in their
experiments the shear rate seems to be increased faster.
To further check if the drops rheological properties inuence
their deformation behavior, we conducted relaxation experiments.
The inuence of an immobilized interface should be negligible in
these experiments because the ow of the dispersed phase results
from the interfacial tension reforming the drop and not from an
external ow. Drops of same size and different inner dispersed
phase concentrations were deformed to a deformation of around
D = 0.2 and observed during relaxation. The ratio of actual to maximum deformation D/Ds dependent on the dimensionless relaxation
time trelax is shown in Fig. 4.
The dependency of deformation ratio D/Ds on dimensionless
relaxation time is the same for double emulsion drops with 1
between 0.35 and 0.60. The elastic properties detected in rheological measurements [29] do not show any inuence on relaxation
behavior. This could, on the one hand, be a result of the elastic properties not being pronounced enough. On the other hand, it could be
possible that the water droplets in the oil drop have enough time to
rearrange during relaxation and are thus not deformed. The elastic properties of emulsions are a result of deformed interfaces. If
the processes of deformation or relaxation are conducted slowly
enough, the droplets can rearrange and thus do not have to be
deformed in order to follow the deformation. No elastic properties of the drop would be detectable, even if they can be measured
in oscillatory rotational measurements.
3.2. Coalescence of inner water droplets with the outer phase
The most important and intriguing phenomenon in the formation and processing of double emulsion W/O/W drops is the
tendency for the innermost droplets to coalesce with the outer
continuous phase uid, thus decreasing the number of the innermost droplets. In order to better understand the mechanism of this
coalescence process, we visually observed non-deformed double
emulsion drops as well as double emulsion drops during deformation and breakup.

A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 336343

341

Fig. 5. Micrographs of a non-deformed double emulsion drop at different time steps. The coalescing inner droplet is marked by a circle. Blow-ups of the circled areas are
shown above the drops.

No single coalescence event was observed during all the breakup

experiments described above. In order to better see any coalescence effects, we performed experiments with the W/O emulsion
containing bigger inner droplets (around 5 m). The observation
of a non-deformed double emulsion drop over a time range of 1 h
did not show any change in the amount of inner water droplets.
Moreover, after deformation and subsequent relaxation of the outer
double emulsion drop, there was no observable change of its lling level. Even during breakup of the double emulsion drops no
coalescence of inner water droplets with the outer phase could be
observed. Loss of inner droplets by coalescence is an often described
and observed phenomenon. Therefore, it was surprising that we
could not observe any coalescence event in our experiments.
Comparing our material system to those used in real emulsication processes, it stands out that we did not use a second surfactant
in the outer phase. For single drop experiments, a hydrophilic surfactant is not mandatory as oil drops do not have to be stabilized
against coalescence with each other. In order to check the hypothesis that coalescence is linked to the presence of an additional
hydrophilic surfactant, we added different hydrophilic surfactants
(Tween 20, Tween 80, Lutensol AT80 or egg yolk powder) to the
outer phase for the following observations.
In fact, coalescence of inner water droplets with the outer phase
was observed in these experiments. Video 1 shows a sequence
where some coalescence phenomena can be observed.
Supplementary material related to this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.colsurfa.
2013.11.043.
Fig. 5 shows an example of a series of pictures of one
non-deformed double emulsion drop in a Tween 20/corn syrup
solution. The experiments with Tween 80 and Lutensol AT80
showed comparable results. The total time scale between the
rst and the last picture is 0.3 s. The rst picture was taken
approximately 2 min after the injection of the drop. Blow-ups of

the part of the drop where coalescence is observable are shown

above the drop pictures.
The black circle and the black arrow mark an inner water droplet
that coalesces with the outer uid in the time frame of observation.
In the rst two pictures (t = 00.07 s), a distinct droplet can be recognized in the bottom right of the circle. In the following pictures,
this droplet can no longer be seen. Moreover, a black shadow which
spreads over the interface of the big oil drop can be seen. This phenomenon results from the ejection of the inner water droplet into
the outer phase. The refractive indices of outer phase and inner
water phase are not the same because of their different compositions (corn syrup vs. salt solution). The coalescence of an inner
salt solution droplet with the outer corn syrup phase leads to a
local change in corn syrup concentration. This, in turn, changes the
refractive index locally, which can be detected as a black shadow
at the oilwater interface. The black shadow thus indicates mixing
of the two phases which can only be a consequence of coalescence
of the inner water droplet to the outer phase.
Video 2 shows the same double emulsion drop during deformation. Again, several inner droplets coalescing with the outer phase
can be observed.
Supplementary material related to this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.colsurfa.
2013.11.043.
Fig. 6 shows a picture series of the same double emulsion drop
during deformation. Again, a coalescing inner water droplet is
marked by a black circle. In the rst two pictures the inner water
droplet can still be observed while it is disappearing in the next
pictures leaving behind a shadow of the mixing uids.
Here, coalescence can be nicely followed. It stands out that loss
of inner droplets by coalescence occurs independently from deformation and breakup of the outer oil drop. Stroeve and Varanasi
concluded from their observations that coalescence takes place
during breakup of double emulsion drops. On the other hand,

Fig. 6. Micrographs of a deformed double emulsion drop at different time steps. The coalescing inner droplet is marked by a circle.

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A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 336343

coalescence in stagnant non-deformed drops was also observed by

Gaitzsch et al. [40].
Another interesting fact is the time scale for the occurrence
of coalescence. The droplets did not disappear immediately after
drop formation, deformation or breakup. While a single coalescence
phenomenon happened in less than a second, these phenomena
took place over a longer time scale. It seems as if the process
of interface-interface approach, lm thinning and rupture takes
from some seconds up to several minutes. This can be important
for understanding coalescence during the production of multiple emulsions. If coalescence times are much higher than typical
process times (which are in fact on the order of milliseconds to
seconds [41]), coalescence is unlikely to happen during the deformation and breakup process but mainly after formation of double
emulsions. This draws attention to the importance of emulsier
choice on multiple emulsion stability. In this study, different surfactants were used. However, comparing their inuence is not
that easy as a distinct quantication of coalescence is not possible in the given experimental setup. Nevertheless, differences were
observable. Using egg yolk powder as natural polymeric emulsier resulted in less coalescence phenomena in the same time
frame than for the surfactants Tween 20 and 80, and Lutensol
AT80. This conrms statements in the literature proposing the
use of proteins in order to achieve better stabilization of double
emulsions [3,25,42].
4. Conclusions
This work aims to investigate deformation and breakup of
W/O/W double emulsion drops with different inner dispersed
phase concentrations 1 in a purely extensional ow. Moreover,
visual observations were conducted enabling us to track coalescence of inner water droplets with the outer continuous phase.
Experiments were conducted in a 4-roll mill device which allows
for deformation of single drops in extensional ow and simultaneous visual observation. For this, inner W/O emulsion drops of
different 1 were prepared. Rheological measurements showed an
increase in viscosity with increased 1 and elastic components in
the ow behavior for 1 0.5.
Visual observations of double emulsion drops during deformation gave qualitative indications of an immobilized interface. The
inner droplets act as tracers of the internal ow and thus allow for
this observation. They do not move during steady state deformation
of a double emulsion drop.
Steady state deformation of drops with different inner dispersed
phase concentrations and drop size ratios between inner and outer
drop did not show any deviations from behavior known from simple Newtonian systems. Moreover, drop shapes were ellipsoidal
independent of the inner dispersed phase concentration and thus
rheological properties of the drop phase. Breakup experiments
showed that tip streaming occurs in all systems. In addition, the
critical Capillary number at which breakup is observable was the
same for all inner dispersed phase concentrations and thus viscosity
ratios. This behavior can be explained by the observed immobilization of the interface. The oil phase contains the surfactant PGPR in
order to stabilize the inner water droplets. The addition of a second
hydrophilic surfactant in the outer aqueous phase did not change
the observations. The ow of the continuous uid transports the
surfactant on the interface toward the ends of the deformed drop.
As a result, interfacial tension varies along the drop interface and
induces Marangoni stresses acting against surfactant transport.
The interface is immobilized. As PGPR is a standard surfactant
for the stabilization of the inner water droplets in W/O/W emulsions, our observations are relevant for a wide range of double
emulsion applications. During the production of W/O/W emulsions
using membrane processes the emulsion drops are directly formed

in the required drop size. But during processing, e.g. pumping, the
emulsion undergoes shearing and elongation. Our results show
that the collision rate of inner droplets with the outer interface
is not inuenced by the ow around the drop because this ow
does not induce an internal ow. This stands in contrast to earlier
attempts to model collision rate in double emulsion drops [43].
Relaxation experiments showed the same relaxation behavior
for all double emulsion drops. The inner dispersed phase concentration did not inuence the relationship between deformation
ratio and relaxation time. This result indicates that the elastic
properties of the inner emulsion are not pronounced enough to
inuence drop deformation and breakup behavior. Another possible explanation is that the inner droplets can rearrange during
relaxation, because relaxation is a quite slow process compared
to breakup in typical emulsication devices. As drop deformation
is the source of elasticity in emulsions, a slow deformation and
relaxation of the outer drop may allow the inner droplets to rearrange in order to follow the outer deformation rather than getting
deformed themselves. This is probably the reason why elastic
behavior was not detectable in all deformation experiments.
Concerning coalescence of inner droplets with the outer phase
it stands out that this phenomenon could only be observed when
a second surfactant was used in the outer phase. The nature of this
surfactant did inuence the time range in which coalescence was
observable. Coalescence time was longer for double emulsions with
egg yolk as polymeric emulsier in the outer phase compared to the
low molecular weight surfactants Tween and Lutensol. This nding
conrms other observations in the literature [3,25,42] showing
that the choice of surfactants for multiple emulsions mainly
inuences their stability. Nevertheless, these observations showed
once more how important it is to better investigate the behavior
of the two surfactants present in double emulsions. It would be
interesting to nd out whether the two surfactants interact with
each other and which one really dominates at the interface.
If coalescence of the inner droplet with the outer phase
occurred, it was observed independently from the degree of drop
deformation, even when outer drops remained non-deformed.
However, we did not observe coalescence during the process of
breakup itself in our experiments. Moreover, there was no typical
position in double emulsion drops, where coalescence of inner
droplets was observed preferably. It seems as if each inner droplet
getting into contact with the oilwater interface coalesces, given
enough time. Considering the time scale for coalescence to occur,
we found that coalescence phenomena are not completed after
several seconds but that they can even be observed after minutes
of observation. This is important information for understanding
the loss of inner droplets by coalescence during the production of
double emulsions. Typical process times for industrial emulsication processes are on the order of some milliseconds to seconds.
Therefore, it could be possible, that most coalescence phenomena
take place after emulsication. As taking samples and analyzing
them also takes some time, instability phenomena measured after
preparation could be wrongly attributed to the emulsion preparation step. This in turn could mean that the emulsication process
itself does not really inuence the loss of inner water droplets by
coalescence. This hypothesis will be pursued in the second part
of this publication (this issue). Moreover, these observations can
be a starting point for developing a model describing coalescence
behavior in multiple emulsions.

Acknowledgements
The authors want to thank KHYS (Karlsruhe House of Young
Scientists) for nancially supporting the research stay at UCSB.
Further on, nancial support by the Federal Ministry of Education

A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 336343

and Research (project 13N10296) within the JointLab IP3, a joint

initiative of KIT and BASF is gratefully acknowledged.
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