Colloids and Surfaces A: Physicochem. Eng.

Aspects 461 (2014) 344351

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 II: Inuence of

emulsication device on release of water by coalescence
Anna Schuch , Jeanette Wrenger, Heike P. Schuchmann
Institute of Process Engineering in Life Science, Section I: Food Process Engineering, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany

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

W/O/W emulsions with comparable

drop sizes produced with different
emulsication devices.
Encapsulation efciencydrop size
relationship independent of emulsication device.
Coalescence seems to occur after
processing.

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
Coalescence
Encapsulation efciency
Production process
Emulsication device

a b s t r a c t
We compare different emulsication devices for the production of W/O/W double emulsions. Rotorstator devices (colloid mill and tooth rim dispersing machine), high pressure homogenization (standard
and modied process) as well as a rotating membrane system were used. For better comparability, we
produce double emulsions of different oil drop sizes with each device by changing process parameters.
A standard double emulsion recipe was chosen for all emulsions.
Encapsulation efciency of water in the double emulsions, measured by DSC technique, is found to be
directly dependent on oil drop size of the double emulsions for each emulsication device. The bigger
the oil drops, the higher is the encapsulation efciency. Double emulsions with comparable oil drop sizes
produced with different devices show more or less the same encapsulation efciency.
This nding indicates that coalescence is mainly inuenced by geometrical parameters like oil drop size.
The differing drop breakup mechanisms in the different emulsication devices do not show any inuence
on encapsulation efciency. It can thus be concluded that loss of inner water droplets by coalescence
mainly takes place after the production process. The choice of the emulsication device does not directly
inuence encapsulation efciency. Conventional high shear devices are as suitable for the production of
double emulsions as membrane processes.
2013 Elsevier B.V. All rights reserved.

1. Introduction

Abbreviations: DSC, differential scanning calorimetry; HPH, high pressure

homogenization; PGPR, polyglycerol polyricinoleate; rpm, revolutions per minute;
SHM, simultaneous homogenization and mixing; W1 , inner water phase; W2 , outer
water phase; 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), 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.2013.11.044

Multiple emulsions are complex liquid multiphase systems.

They are also called emulsions of emulsions because the dispersed
phase of these emulsions consists of an emulsion itself. In waterin-oil-in-water (W/O/W) emulsions water droplets are dispersed
in an oil phase which itself forms drops in a continuous water
phase. This complex structure enables the use for different applications ranging from separation processes [1] and encapsulation of
specic molecules for cosmetic, pharmaceutical, agrochemical and
food products to fat reduction in food [26].

A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 344351

Nomenclature
Symbols
D
EE
1
2

x50.3

diameter of the orice [m]

encapsulation efciency
inner dispersed phase concentration
outer dispersed phase concentration
shear rate [s1 ]
mean droplet size [m]

Comparable to macroemulsions these systems are thermodynamically unstable. Their structure can change due to different
phenomena [7,8]. On the one hand, water molecules can diffuse
from the inner water phase (W1 ) to the outer water phase (W2 ) or
vice versa. These processes change the amount of water encapsulated in the oil droplets. On the other hand, coalescence phenomena
can occur. As in single water-in-oil emulsions, the oil droplets
can coalesce. Moreover, coalescence between two W1 droplets or
between W1 droplets and the W2 phase can change the structure
of double emulsions. Especially the last coalescence phenomenon
inuences the amount of water encapsulated in the oil droplets and
is thus crucial for the functionality of double emulsions. All these
instabilities can occur during processing as well as during storage
of the emulsions.
In order to control the structure of double emulsions two
step processes are usually used [9,10]. For the production of a
W1 /O/W2 emulsion a so-called inner water-in-oil (W1 /O) emulsion is formed rst. Size and amount of inner water droplets can
thus be controlled. High shear devices like rotor-stator devices
and high-pressure homogenizers are used most often in order to
produce small water droplets which have been shown to increase
double emulsion stability [3]. In a second emulsication step, this
inner emulsion is used as dispersed phase of the nal double emulsion. That means that drops of the W1 /O emulsion having the
desired drop size are directly formed or produced by further disruption of big drops in a continuous aqueous phase (W2 ). This
step is very important for the quality and functionality of the nal
W1 /O/W2 double emulsions. During processing of the double emulsion drops, the above mentioned instabilities can occur and thus
inuence emulsion structure [11]. Especially coalescence of inner
droplets with the outer water phase reduces the amount of water
encapsulated in the double emulsion, what is crucial for all double
emulsion applications.
Emulsication devices can be divided into drop forming techniques, where drops are directly formed having the desired size,
and high shear techniques, where bigger drops are rst formed
and then further broken up by the intense ow conditions of the
continuous phase.
In conventional emulsication devices like rotor-stator systems
and high pressure homogenizers, big drops of the dispersed phase
are ruptured due to the ow of the external phase in the device.
In colloid mills the governing ow is laminar and turbulent shear
ow, dependent on process parameters [12]. Tooth-rim dispersing machines, another rotor-stator device, induce mainly shear and
elongational ow [13]. In high pressure homogenizers drops are
mainly broken up by inertia in turbulent ow and due to cavitation
[14,15]. It is reported, that during deformation and breakup of double emulsion drops the inner water droplets can get lost into the
outer water phase by coalescence [16]. An increase of shear rate in
a Couette device was found to increase the release of salt encapsulated in the inner phase of a W/O/W emulsion by coalescence [17].
In a former work we showed that the same is true for drop breakup
in a colloid mill. The higher the applied shear rate, the lower the
encapsulation efciency. The encapsulation efciency EE is dened

345

as the amount of water in the nal double emulsion related to the

amount of water theoretically encapsulated.
Moreover, it was shown that the encapsulation efciency correlates with the size of the double emulsion drops [18].
Membrane emulsication is in general described to produce
double emulsions with lower release of encapsulated water
compared to conventional emulsication devices [19,20]. The
advantage of membrane emulsication with regard to multiple
emulsions production is the slow formation of emulsion drops
at the surface of the membrane. The nal drop size of the emulsion is achieved directly. The double emulsion drops are not
exposed to high shear stresses during production and are not
further broken up. Moreover, narrow size distributions of the emulsion drops can be achieved using membrane techniques compared
to using conventional high shear devices [2124]. Nevertheless,
membrane emulsication techniques still show some disadvantages considering the production of big amounts of emulsions. The
ux per square meter of membrane is very low (between 5 and
250 l m2 h1 ) compared to uxes of conventional emulsication
devices (100010,000 l h1 ) [21]. A relatively new emulsication
device that tackles this problem is the rotating membrane emulsication device [25]. The rotation of the membrane itself increases
wall shear stresses and ux through the membrane and thus allows
for shorter production times. Another challenge concerning membrane processes is life time of the membranes. Life time can be
short as fouling, what means blocking of the membrane pores by
emulsion ingredients, can occur. It is thus desirable to nd an emulsication device with high throughput that enables the production
of W/O/W emulsions with high encapsulation efciencies.
The encapsulation efciencies measured by different research
groups using different membrane techniques (cross-ow, premix
membrane emulsication, microchannel emulsication) for the
production of W/O/W emulsions were reported to be higher than
90% [24,26]. Nevertheless, a comparison of the production of double
emulsions by Pawlik et al. using two membrane techniques and a
high shear Silverson mixer showed that depending on the process
parameters the release of inner water drops can even be higher
for cross-ow emulsication than for the high shear mixer [27].
Moreover, comparing a stirring method and membrane emulsication Okochi et al. did not observe any difference in encapsulation
efciency for emulsions with the same oil drop size [28]. Dickinson et al. compared a high pressure homogenizer and a high
shear mixer and found lower encapsulation efciencies for the
high pressure process at comparable oil drop sizes [29]. As some of
these observations made by different research groups are contradictory it is desirable and necessary to directly compare different
emulsication devices for the production of multiple emulsions.
Unfortunately, a comparison of results from different authors is
nearly impossible. On the one hand, the material system used for
the preparation of double emulsions does strongly inuence their
stability. Diffusion processes as well as coalescence is inuenced by
the composition of both aqueous phases, the nature of the oil phase
and the nature and concentration of the hydrophilic and lipophilic
surfactants used [30,31]. In addition, size and amount of inner
water droplets inuence coalescence phenomena [30]. Moreover,
the characterization of double emulsions in terms of encapsulation efciency is not easy. Different authors use different, mostly
indirect measurement techniques to determine the encapsulation
efciency. The results of these techniques have been shown to differ
in a wide range [32].
Another indication that makes the comparison of different
emulsication devices for double emulsion production necessary
comes from the visual observation of double emulsion drops during
deformation and breakup shown in the rst part of this publication. Loss of inner water droplets into the outer water phase by
coalescence was observed in non-deformed as well as in deformed

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A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 344351

double emulsion drops. As coalescence was observed independent

from drop deformation, it is most likely to occur in membrane processes as well as in conventional high shear devices. Moreover, the
time scale for coalescence to occur was found to be in the range of
seconds to minutes. Residence times of emulsion drops in typical
high shear emulsication devices are in the range of milliseconds
to seconds [33]. It could thus be possible that coalescence in double emulsions mainly occurs after their preparation. This in turn
would mean that the emulsication process itself does not mainly
inuence coalescence in double emulsions.
To follow these indications we compare different emulsication devices for the production of W/O/W double emulsions in the
present work. We produce W/O/W emulsions with the same composition using different methods and varying process parameters.
Two rotor-stator systems (colloid mill and tooth-rim dispersing
machine) a high pressure homogenizer with two different process
setups and a membrane emulsication device (rotating membrane)
are used. The encapsulation efciencies were determined using
a direct measurement technique based on differential scanning
calorimetry (DSC). These boundary conditions allow for a comparison of the different methods.
2. Materials and methods
The composition of the double emulsions was the same in all
experiments. First, a so called inner W/O emulsion was produced.
For double emulsions produced in rotor-stator systems and normal high pressure processes, pre-emulsions consisting of big W/O
drops in the continuous water phase were formed prior to real
emulsication. These steps as well as emulsication processes and
characterization methods are described below.
2.1. Preparation of inner W/O emulsions
The continuous oil phase of the W/O emulsions consisted of
canola oil (Floreal Haagen, Germany) and polyglycerol polyricinoleate as surfactant (PGPR 4175, Paalsgard, Denmark). After
dissolving 5 wt% of the surfactant in oil, the dispersed water phase
was slowly added. This emulsion premix was stirred till a homogeneous emulsion with droplet sizes around 10 m was obtained. The
dispersed phase consisted of demineralized water and 0.5% NaCl
(Carl Roth GmbH & Co, Germany). The salt was used in order to
suppress Ostwald ripening in the double emulsion by balancing the
Laplace pressure with an increased osmotic pressure of the inner
water phase [34,35]. The dispersed phase concentration of these
emulsions was 1 = 0.3. 300 g of the premix were further homogenized using a lab scale colloid mill IKA magicLAB modul MK (IKA
Stauffen, Germany). The gap width between rotor and stator 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 production process of
the inner emulsions was the same for all experiments performed.
The sizes of the water droplets were between 0.05 and 0.8 m
with a median x50.3 = 0.3 m. The size distribution of these emulsions can be found in our previous publication [18].
2.2. Preparation of pre-emulsions
The continuous phase of all double emulsions consisted of the
same materials. 3 wt% of the surfactant egg yolk powder (pasteurized and spray dried Sanovo, Germany) were dissolved in
demineralized water.
Pre-emulsions were prepared for the emulsication process
with rotor-stator devices as well as with normal high pressure
homogenizer. While stirring the continuous phase with a propeller
stirrer, the dispersed phase (inner emulsion) was slowly added till
a dispersed phase concentration of the double emulsion of 2 = 0.3

was achieved. The size of the double emulsion drops in this premix
was around 100 m.
2.3. Preparation of W/O/W emulsions using rotor-stator devices
W/O/W emulsions were produced using two different geometries both connected to the lab scale rotor-stator device IKA
magicLAB : a colloid mill (modul MK) and a tooth rim dispersing
machine (modul UTL).
Using the colloid mill, the gap between rotor and stator was
manually set to 0.32 mm. The rotational speed was varied in
the range between 5000 and 15,000 rpm. For each emulsication
experiment the pre-emulsion passed through the gap of the device
two times.
Using the tooth rim dispersing machine the rotational speed
was varied between 7000 and 20,000 rpm. The emulsions were produced by double passage of the pre-emulsion, comparable to the
production in the colloid mill.
2.4. Preparation of W/O/W emulsions using high pressure
homogenizers
For emulsication in high pressure homogenizers (HPH) a preemulsion is generally pumped through a dispersing unit by a high
pressure pump. Normally, drop breakup mainly occurs in the ow
downstream of the dispersing unit.
In order to check if droplet disruption takes also place inside
the high pressure pump, the pre-emulsion of the double emulsion
was rst only pumped without the use of any dispersing unit. A
three-piston pump 53MC4 (APV Gaulin GmbH, Germany) was used.
The drop size distribution as well as encapsulation efciency of the
emulsion after pumping was measured.
W/O/W emulsions were then produced using a conventional
HPH process with a one-piston pump (M-110EH, Microuidics,
USA) and simple round-shaped orices of different hole diameters (0.6 and 0.8 mm). The pressure applied for emulsication was
around 10 bar for the 0.8 mm orice and around 50 bar for the
0.6 mm orice. The emulsions passed the high-pressure homogenizer once.
Moreover, experiments were performed using the SHM (simultaneous homogenization and mixing) setup, a modied HPH
process [36]. For this, the continuous outer water phase (W2 ) was
pumped through the orice (diameters d: 0.8 and 0.4 m) by the
same three-piston pump as used before (53MC4). Depending on
the orice and the volume ow the pressure in front of the orice
was between 7 and 270 bar. The inner emulsion (W1 /O) was added
directly behind the orice using a Mohnopump (VARMECA37M,
Erich Netzsch GmbH & Co. Holding KG, Germany) as depicted in
Fig. 1. It is shown that drops are deformed and broken in the free
jet developing in the region used for inserting the inner emulsion
[37]. The volume ow of the dispersed phase was adapted to the
ow through the orice in order to adjust a mixing ratio of 1:1.
The outer dispersed phase concentration of the double emulsion
2 was thus 0.5.
2.5. Preparation of W/O/W emulsions using a rotating membrane
device
Double emulsions of different drop sizes were produced using
the rotating membrane device Megatron MM 1-56 (Kinematica AG,
Switzerland). For emulsication in the rotating membrane device
the formation of a pre-emulsion is not necessary. The dispersed
phase of the nal emulsion, in this case the inner W/O emulsion,
was directly conveyed through the membrane. The membrane used
is made from mesh wire with a mean pore size of 2.5 m. The continuous W2 -phase was pumped through the gap between rotating

A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 344351

347
1,0

characteristic drop size x50,3 [m]

Fig. 1. Scheme of the emulsication process with SHM method. The drops are
formed and broken up behind the orice and thus do not pass the high pressure
pump.

membrane and outer cylinder. Both phases were pumped using a

peristaltic pump (lap pump 323, Watson Marlow, USA). The volume
ow of the dispersed phase was 43.6 g/min, the one of the continuous phase 124.1 g/min. Therefore, the outer dispersed phase
concentration of the double emulsion was 2 = 0.26. In order to
produce double emulsions with different drop sizes, the rotational
speed of the membrane was varied between 5000 and 9000 rpm.
2.6. Measurement of drop size distributions of the double
emulsion
The outer (oil) drop size distributions of the W/O/W double
emulsions were measured using static laser light scattering. Measurements were conducted with LS 13320 (Beckman Coulter Inc.,
USA). Drop sizes were calculated using Fraunhofer model and the
refractive index of the continuous phase was set to 1.333.
The measurement cell of the device was lled with demineralized water. The emulsions were diluted directly before introducing
them. All measurements were performed three times and the mean
distributions were calculated. The median x50,3 was used as characteristic drop size of the double emulsions.
2.7. Measurement of encapsulation efciency (EE) using DSC
The encapsulation efciencies of the double emulsions were calculated using the results of differential scanning calorimetry (DSC)
measurements [38]. A DSC 8000 (Perkin Elmer, USA) was used.
Samples of 712 mg were lled in aluminum pans and sealed hermetically. The samples were cooled from 10 C to 60 C at a cooling
rate of 2.5 K/min. Using the specic heat of freezing of the inner
water droplets, the amount of water in the inner droplets of the
double emulsions were calculated. Details of the method can be
found elsewhere [38]. The encapsulation efciency EE is dened
as the amount of water present in the inner water phase mW1 (t)
divided by the theoretical amount of inner water (according to the
recipe) mW1 (t0 ) and is calculated as follows:
EE =

mW1 (t)
mW1 (t0 )

(1)

3. Results
3.1. Production of W/O/W emulsions in rotor-stator devices
Double emulsions of different oil drop sizes were produced in
the colloid mill by varying the rotational speed of the rotor. Resulting median diameters x50.3 and encapsulation efciencies EE were
measured and are shown in Fig. 2. The time between production of

encapsulation efficiency EE
60

50

0,8

0,6

40
0,4
30
0,2
20

10
4000

6000

8000

10000

12000

14000

encapsulation efficiency EE [-]

drop size x50,3

70

0,0
16000

rotational speed n [rpm]

Fig. 2. Droplet sizes x50.3 and encapsulation efciencies EE of W/O/W emulsions
produced in a colloid mill applying different rotational speeds n.

the emulsions and measurement was at least 20 min. As repeated

measurements of the same sample do not show signicant changes
in EE (results not shown here) we presume that loss of water by
coalescence is completed after those 20 min.
The characteristic drop size x50.3 as well as the encapsulation
efciency EE of the double emulsion drops decrease with increasing
rotational speed. The highest encapsulation efciencies are around
0.8 while the lowest are around 0.25. Drop sizes decrease from
around 57 m to 20 m. Lower encapsulation efciencies correlate
with lower double emulsion drop sizes. Mean values and standard
deviations of EE are exemplarily shown for double emulsions produced at 5000, 7000 and 10,000 rpm. The standard deviations of
three measurements are between 0.03 and 0.05. These values are
representative for the measurement technique and can thus be
adopted for all double emulsions.
The predominant ow in the colloid mill is shear ow. Increasing
rotational speeds correlate with increasing maximum shear rates
in the emulsication device. The shear rate can be calculated using
the rotational speed as well as the gap width of the device. It varies
between 24,000 and 74,000 s1 in the experiments. This means that
encapsulation efciency decreases with increasing shear rates and
with decreasing droplet sizes of the oil drops. The tendency that
higher shear rates lead to higher release rates of double emulsions
was also observed by Muguet et al. [39]. A correlation between
drop sizes and encapsulation efciency was already observed in
our former work [18].
Tooth rim dispersing machines are another kind of rotor-stator
device used for emulsication. Shear as well as elongation dominates the ow pattern inside the device which leads to drop
breakup. Again, double emulsions of different oil drop sizes were
produced by applying different rotational speeds during emulsication. Comparable to Fig. 2 drop sizes and encapsulation
efciencies of the double emulsions are shown in Fig. 3.
Characteristic drop size x50.3 as well as encapsulation efciency
EE decrease with increasing rotational speed. Moreover, it stands
out that oil drop size and encapsulation efciency decrease in the
same manner comparable to the results from the experiments in
the colloid mill. Smallest oil drop sizes are around 15 m. These
double emulsions have an encapsulation efciency of around 0.12.
The highest encapsulation efciency is around 0.55. It results from
the lowest rotational speed applied at 7000 rpm. The shear rate
increases with increasing rotational speeds. But as the ow inside
the tooth rim dispersing machine is not a pure shear ow, the calculation of shear rates is not as simple as for colloid mills. Moreover,
it is not clear in which extent the elongational ow contributes to

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1.0

encapsulation efficiency EE

0.8

60
0.6
50
40

0.4

30
0.2
20

8000

10000

12000

14000

16000

18000

0.0
22000

20000

drop breakup. However, elongational stresses do also increase with

rotational speed.
For the direct comparison of the different rotor-stator devices
we thus display the encapsulation efciency of the double emulsions (already shown in Figs. 2 and 3) dependent on their oil drop
size in Fig. 4.
The encapsulation efciency increases with increasing oil drop
sizes for both rotor-stator systems. Moreover, the encapsulation
efciencies of double emulsions with the same oil drop sizes produced with the different devices are comparable. The maximum
difference in encapsulation efciency for double emulsion drops of
the same size is around 0.1 which is in the range of expected deviations in the measurement, known from the results shown in Fig. 2
and from other investigations with the same materials [18].
3.2. Production of W/O/W emulsions using high pressure
homogenizer (HPH)
In high pressure homogenizers drops are predominantly broken
up in turbulences developing in the ow or by cavitation induced
ow. As the drop breakup mechanism is not the same as in rotorstator systems, differences in the suitability to produce multiple
emulsions are to be expected. Especially cavitation could lead to
increased release of water of the double emulsions by evaporation.
1.0

Encapsulation efficiency EE [-]

80

60

40

20

0,1

Fig. 3. Droplet sizes x50.3 and encapsulation efciencies EE of W/O/W emulsions

produced in a tooth rim dispersing machine applying different rotational speeds n.

colloid mill
tooth rim dispersing machine
0.8

0.6

0.4

0.2

0.0
40

after pump passage

smallest drop size
after colloid mill

rotational speed n [rpm]

20

cumulative size distribution Q3 [%]

drop size x50.3

70

10
6000

100

encapsulation efficiency EE [-]

characteristic drop size x50.3 [m]

80

60

characteristic drop size x50.3 [m]

Fig. 4. Encapsulation efciency EE dependent on oil droplet diameter x50.3 for double
emulsions produced with colloid mill and tooth rim dispersing machine.

10

100

diameter x [m]
Fig. 5. Comparison of droplet size distributions of W/O/W emulsions produced
in a colloid mill and in a three-piston pump, as usually applied for high pressure
homogenization devices.

In order to compare the results from high pressure homogenization

with those from rotor-stator systems, double emulsion drops in the
same size range have to be produced.
The mechanical stress in high pressure homogenizers is known
to be generally higher than in normal rotor-stator devices. The process is thus frequently used in order to produce very small drops.
On the one hand the stress in the pump can be quite high on the
other hand the ow behind the orice is known to determine the
nal drop sizes.
In order to investigate the inuence of the pump on drop
breakup and release of water, we conducted an experiment conveying the double emulsion premix through the pump and measuring
drop size distribution and encapsulation efciency afterward. Fig. 5
shows cumulative size distributions of a W/O/W emulsion after
the passage of the three piston pump and after preparation in the
colloid mill at highest shear rate.
It can be seen, that the drop sizes of the double emulsion that
passed through the pump are even smaller than the smallest drops
produced in the colloid mill. The encapsulation efciency of this
double emulsion was zero. All the inner water droplets got lost
into the outer water phase during pumping. Therefore, it is not
possible to produce double emulsions with this high pressure pump
for comparison of the different devices.
In order to produce double emulsions with bigger drops by
high pressure homogenization we followed two paths. On the
one hand we used a one-piston pump and an orice as homogenization apparatus. On the other hand we used the three-piston
pump but conducted the experiments following the SHM method
as described in Section 2.4. The encapsulation efciencies of these
double emulsions dependent on the resulting oil drop size are
shown in Fig. 6. As the shear stresses in a high pressure homogenizer are not easy to measure or calculate, we use this way of
presentation and comparison again.
The drop sizes of the emulsions produced by the normal high
pressure homogenizer, using a conventional orice valve, through
which the emulsions are pumped for break-up, are around 10 m
in size. The encapsulation efciency of these emulsions is smaller
than 0.1. It was not possible to produce bigger double emulsion
drops using this emulsication device and the available orices.
With the SHM method, however, it was possible to produce double
emulsions in a size range between 10 and 60 m. Here, the inner
emulsion droplets do not pass the pump and the narrow gap of the
orice valve. The encapsulation efciency increased in this range
with increasing drop sizes. Maximum encapsulation efciency was

A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 344351

1.0

1,0

Encapsulation efficiency EE [-]

High pressure homogenizer (one-piston pump)

High pressure homogenizer - SHM
encapsulation efficiency EE [-]

349

0.8

0.6

0.4

0.2

0.0

colloid mill
tooth rim dispersing machine
HPH-SHM
HPH
rotating membrane

0,8

0,6

0,4

0,2

0,0
20

40

60

characteristic drop size x50.3 [m]

Fig. 6. Encapsulation efciency EE dependent on oil droplet diameter x50.3 for double
emulsions produced with a high-pressure homogenizer, using a conventional orice
valve (lled symbols) as well as SHM method (open symbols).

20

40

60

80

characteristic drop size x50.3 [m]

Fig. 8. Encapsulation efciency of W/O/W emulsions dependent on their oil drop
size: comparison of different emulsication devices.

achieved for the biggest double emulsion drops (around 0.6). The
outer dispersed phase concentration 2 of the double emulsions
was not the same in both processes, but additional experiments in
a colloid mill could conrm that the outer dispersed phase concentration does not inuence the relationship between drop size and
encapsulation efciency. These results can be found in supplementary material.
Smaller double emulsion drops are obviously a result of higher
energy input and thus higher shear stresses and higher turbulent
intensity. That means that higher shear stresses result in smaller
drops and thus lower encapsulation efciencies of the double emulsions.

Encapsulation efciencies are again depending on the oil drop

sizes of the double emulsions. The smaller the oil drops, the lower
the encapsulation efciency. Maximum encapsulation efciency
is around 0.55 for a double emulsion with oil drop sizes around
48 m. Maximum shear rate in the device was calculated in order
to check whether drops are in fact formed at the surface of the membrane and not broken up in the ow between rotating membrane
and housing of the device. Maximum shear rate in the membrane device leading to the smallest emulsion drops was around
13,000 s1 . As minimum shear rate in the colloid mill (24,000 s1 )
lead to oil drop sizes around 66 m it can be concluded that drops
were not broken up in the membrane device but in fact generated
through the membrane pores.

3.3. Production of W/O/W emulsions using rotating membrane

emulsication

3.4. Comparison of different emulsication devices and

discussion of the results

Using the rotating membrane device double emulsions of different oil drop sizes were produced by changing the rotational speed
of the membrane. Encapsulation efciencies dependent on oil drop
sizes are shown in Fig. 7.

Fig. 8 compares the dependency of encapsulation efciency of

W/O/W emulsions on their drop size for the production in different
emulsication devices.
The comparison of the results from different emulsication
devices clearly shows the same trend for all systems. The encapsulation efciency is predominantly dependent on the oil drop
size. The bigger the oil drops the higher is the encapsulation efciency. The deviations between results from different devices are
in the range of expected deviations of the measurement method.
These results seem to explain some further observations by different research groups. For example Pawlik et al. observed that
applied process parameters determine whether double emulsions
prepared in membrane processes show higher encapsulation efciencies than emulsions prepared in a high shear device [27].
Okochi et al. found comparable encapsulation efciencies of double emulsions with the same oil drop size produced with a stirring
method and a membrane process [28]. The lower encapsulation
efciencies of double emulsions of the same size after high pressure homogenization compared to a high shear mixer could not be
conrmed in our experiments [29].
4. Conclusions

Fig. 7. Encapsulation efciency EE dependent on oil droplet diameter x50.3 for double
emulsions produced with rotating membrane device.

The production of double emulsions is still a challenge as the

inner droplets can get lost into the outer phase by coalescence during breakup of the outer drops. In literature, membrane processes
are described to show better results in double emulsion production

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A. Schuch et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 461 (2014) 344351

in terms of encapsulation efciencies than conventional high shear

devices [19,20]. This is explained by lower shear stresses during the processing and the membrane process thus being gentler.
Unfortunately, membrane processes show some disadvantages for
industrial processes. Low throughputs and short lifetimes caused
by membrane blocking are observed. It would thus be desirable to
nd an alternative method to produce double emulsions showing
comparable emulsion properties.
The present work compares different emulsication devices for
the production of W/O/W double emulsions. Rotor-stator devices
(colloid mill and tooth rim dispersing machine), high pressure
homogenization (standard and SHM setup) as well as a membrane system (rotating membrane device) are used and the process
parameters are varied in a wide range in order to produce double
emulsions of different drop sizes.
For the comparison we used the same material system for all
emulsication devices. The same surfactants, oils and inner emulsions were used as these parameters are known to inuence double
emulsion stability. After producing the double emulsions, oil drop
size distributions as well as encapsulation efciencies of water
in the double emulsions were determined. The ow patterns in
the different emulsication devices are not easily comparable. We
thus compared the results using oil drop sizes and encapsulation
efciencies.
Encapsulation efciency was found to be strongly dependent on
oil drop size for the production in all emulsication devices, independent of shear stresses applied. Higher encapsulation efciencies
correlate with bigger oil drop sizes. Moreover, double emulsions of
the same oil drop size but produced with different devices show
comparable encapsulation efciencies. This nding indicates that
the choice of the emulsication device does not directly inuence
stability of the double emulsions. It thus contradicts the general
assumption that membrane processes are more suitable for the production of multiple emulsions than conventional high shear devices
[19]. Observations by Okochi et al., who did not nd a difference in
EE of double emulsions produced with a stirring and a membrane
method, are conrmed by our results [28]. In contrary, lower encapsulation efciencies of double emulsions of the same size resulting
from the use of a high pressure homogenizer in comparison to a
high shear mixer, as observed by Dickinson et al. were not observed
in the present work [29]. But it was found that the emulsion drops
can be very small leading to total release of the inner water phase,
depending on the pump used. Decreasing oil drop sizes correlate in
our experiments with higher energy input and higher shear rates in
the devices. The higher the energy input and shear rates, the lower
the encapsulation efciencies of the double emulsions. The same
tendency was found by Muguet et al. for experiments in a Couette
device [40]. They did not measure oil drop sizes, but oil drop sizes
should decrease with increasing shear rate [41] what means that
the results show the same tendency as our work.
This independency of the encapsulation efciencies of double
emulsions from their production process underlines the assumption that coalescence mainly takes place after the production
process. Visual observations of coalescence in single double emulsion drops (rst part of this publication) showed that coalescence
phenomena occur in a time range of seconds to minutes while the
residence time of drops in an emulsication device is only milliseconds to seconds. Moreover, coalescence was not only observed
during deformation and breakup of double emulsion drops but also
in non-deformed drops. The process parameters as ow conditions
and process times leading to double emulsions of the same drop size
are not the same for the different emulsication devices. We thus
conclude that the process parameters do only indirectly inuence
coalescence in double emulsions as they inuence the resulting
double emulsion drop sizes. The coalescence process does mainly
take place after double emulsion production and is thus stronger

inuenced by geometrical parameters like inner and outer drop

sizes and dispersed phase concentrations than by process parameters.
For the production of double emulsions in great quantities for
example for applications in food products, this is a very important nding. While the production with membrane devices is much
more time and maintenance consuming than conventional high
shear processes, the resulting product properties are the same.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.colsurfa.
2013.11.044.
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