Research Article

Regimes of Multiple Emulsions of W

1
/O/W
2
and O
1
/W/O
2
Type in the Continuous
Couette-Taylor Flow Contactor
The flow regimes of multiple emulsions in the continuous Couette-Taylor flow
(CTF) contactor and characterization of the dispersion state are reported. The
proposed method of multiple emulsion preparation is a one-step procedure on
the contrary to the classical two-step procedure. The effect of operating para-
meters in the CTF contactor on multiple emulsion appearance, structure (drop
size and packing), and rheological behavior is discussed. The key factors affecting
multiple emulsion preparation in the CTF apparatus were the phases ratio, the
rotational flow, and an annular gap width. The influence of an axial flow was
more significant in the range of small rotational rates. The operating conditions
were optimized to find the best characteristic multiple emulsions (largest inter-
facial area). The paper presents the same exemplary data of using W
1
/O/W
2
emulsions as emulsion liquid membranes (ELMs) in the extraction process and
O
1
/W/O
2
for control active agent (drug) release.
Keywords: Couette-Taylor flow contactor, Emulsion liquid membrane, Multiphase system,
Multiple emulsion
Received: May 29, 2009; revised: August 25, 2009; accepted: October 7, 2009
DOI: 10.1002/ceat.200900278
1 Introduction
Multiple emulsions have been officially defined as systems
composed of inner and membrane phases dispersed into an
outer continuous phase. Among multiple emulsions exist two
types, either with the same or different content of inner and
outer phases.Emulsions of the first type are: water-in-oil-in-
water (W/O/W: inner/membrane/outer) and oil-in-water-in-
oil (O/W/O). The emulsions W
1
/O/W
2
and O
1
/W/O
2
repre-
sent the second type. The more complex possible forms of the
multiple emulsions, e.g., O
2
/W/O
1
/W/O
2
or O
1
/W/O
1
/W/O
2
,
are discussed in [1]. There are also forms of multiple emul-
sions with coexistence of the same phases of different hydro-
phobity or hydrophility degree, e.g., W
1
/W
2
/W
3
, O
1
/O
2
/W, or
W/O
2
/O
1
. Multiple emulsions as high-value products have a
great industrial and medical potential and have been widely
applied. The summarized knowledge on multiple emulsions is
presented in [2]. Multiple emulsions find applications in con-
trolled or sustained drug delivery, targeted delivery, taste
masking, bioavailability enhancement, enzyme immobiliza-
tion, and removing of toxic, radioactive, and organic compo-
nents [2, 3]. Multiple emulsions have also been employed as
intermediate step in microencapsulation processes and are
systems of increasing interest for oral delivery of hydrophilic
drugs, which are unstable in the gastrointestinal tract, like,
e.g., proteins and peptides [4]. Stability and appearance of
multiple emulsions depend on the preparation techniques and
stabilization approaches. For the production of multiple emul-
sions it is important to use a device with flow field, creating
not a large but uniform shear stress to prevent disruption of
the internal droplets and coalescence with the external phase.
Attempts to eliminate drop breakup (leakage) include the ad-
dition of combinations of surfactants or use of polymeric vis-
cous components to reduce the solute permeability through
the membrane phase of emulsions. Multiple emulsions are pre-
pared by either traditional two-step stirring emulsification
methods or more nonconventional ones, such as inversion, or
membrane and microchannel emulsification which are rela-
tively novel methods [5]. In traditional tank mixing, the ener-
gy dissipated per unit volume is nonuniform with the regions
of high shear stresses needed to decrease the droplet size but
causes deformation and bursting of some of the emulsion
drops from the created population. This study presents a one-
Chem. Eng. Technol. 2010, 33, No. 1, 113120 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Ewa Dluska
1
Agnieszka Markowska-
Radomska
1
1
Warsaw University of
Technology, Faculty of
Chemical and Process
Engineering, Warszawa,
Poland.

Correspondence: Dr. Ewa Dluska (E.Dluska@ichip.pw.edu.pl), Warsaw

University of Technology, Faculty of Chemical and Process Engineering,
Warynskiego 1, PL-00-645 Warszawa, Poland.
Multiple Emulsions 113
step preparation method of W
1
/O/W
2
and O
1
/W/O
2
emul-
sions in a continuous Couette-Taylor flow (CTF) apparatus.
The emulsification method related to the O
1
/W/O
2
emulsions
is presented in [6]. In the CTF pattern, the shear stresses are
reduced by one to two orders of magnitude compared to a
stirred tank with similar power input per unit volume and
equal rotor and tank stirrer diameter. This is a result of an in-
crease of the area subjected to a constant maximum shear de-
fined by friction drag on the larger cylinder surface of the CTF
apparatus. The CTF occurs between two coaxial cylinders, one
is rotating, as the conjugation of an axial Poiseuille flow and a
rotating Couette flow, respectively, with induced instability
called the Taylor-vortex above the critical value of rotor rota-
tion frequency. The CTF, also named a helical one, is a rare
flow variation combining intense local mixing with a limited
axial dispersion due to hydrodynamic flow instability resulting
in the creation of vortices. Problems of mixing and dispersion
effects are presented in [7, 8]. The equipment based on the
CTF has a great potential in chemical, nuclear, and biotechnol-
ogy processes especially in multiphase systems. This flow has
been extensively investigated during the past 80 years. The
CTF-based apparatus offers several advantages in industrial
processes: (i) intense local mixing with a limited axial disper-
sion of the phases [9], (ii) high values of heat transfer coeffi-
cients form the surface of the outer cylinder, (iii) indepen-
dence of the residence time from the mixing intensity [10],
(iv) positive influence of the shear stress on rheological prop-
erties of the suspension (emulsion), causing reduction of the
flow resistance, short residence time, low holdup volumes, and
flexible phase ratios. The hydrodynamics and mass transfer of
the two-phase systems have successfully been investigated in
membrane and gap CTF reactors: gas-liquid [1114] and
liquid-liquid systems [6, 15, 16]. The experiments indicated
high values of the volumetric mass transfer coefficients
in the gas-liquid system (k
L
a = 10
1
s
1
) and high overall
mass transfer coefficients being on the order of
k
L
a = 10
2
s
1
for the liquid-liquid system. A specif-
ic interfacial area measured in the CTF two-phase
reactor is 10
3
m
2
m
3
[17, 18] and is an order of
magnitude higher than those which are typical for
a stirred tank reactor. Due to the properties of the
CTF, especially in the multiphase system, its use
for emulsification processes is recommended. The
purpose of the present work is to characterize the
appearance and behavior of multiple emulsions
under flow conditions in the continuous CTF
contactor. The paper presents also exemplary data
of using multiple emulsions of W
1
/O/W
2
type
as emulsion liquid membranes (ELMs) in the pro-
cess of extraction with chemical reaction and an
O
1
/W/O
2
type for control drug release. Details of
preparation of the O
1
/W/O
2
emulsions type en-
trapping an active agent for the release process are
presented in [6]. In the case of extraction by ELMs
in the CTF contactor, the process integrates multi-
ple emulsion formation and extraction in one
apparatus.
2 Scope of Experimental and Procedure of
W
1
/O/W
2
and O
1
/W/O
2
Preparation in
the CTF
The scopes of this work included: choice of a suitable emulsion
system composition and determination of the flow field
parameters in the CTF (helical) apparatus, their effect on the
regimes of multiple emulsion appearance and characteristics,
i.e., stability, mean drop size, and drop size distribution of in-
ternal and membrane phases as well as apparent viscosity. The
processing variables were: rate and ratio of the phases volu-
metric flow, annular gap size, and intensity of the rotational
flow. The factors affecting multiple emulsion preparation in
helical apparatus were optimized to find operating conditions
related to the stable multiple emulsions characterized by the
largest interfacial area, i.e., when the mean drop sizes of the
membrane and internal phases are adequately reduced and by
the greatest packing of the membrane phase drops by internal
phase drops. The one-step emulsification process was carried
out in the continuous CTF contactor. As shown in Fig. 1, two
liquid streams, namely the membrane and the inner phases,
were separately introduced into the annular gap between the
coaxial cylinders of the CTF contactor at the inlet cross sec-
tion, followed by the stream of the outer phase, using precision
pumps. In the CTF contactor run the inner phase was incorpo-
rated as the droplets into the membrane phase drops dispersed
in the outer continuous phase of multiple emulsions. After
steady state achievement in the CTF contactor, multiple emul-
sion samples were collected and analyzed. The operating pa-
rameters in the CTF contactor are summarized in Tab. 1. The
composition of the multiple emulsions according to the speci-
fication of phases (inner, membrane, and outer) is presented
in Tab. 2. The drop size distribution of multiple emulsions was
analyzed using the confocal laser scanning microscope LEXT
OLS3100 and system optical microscope BX-60 Olympus con-
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Figure 1. Experimental setup of multiple emulsion preparation by the one-step
process: continuous CTF contactor (1), inner liquid phase tank (2), membrane
liquid phase tank (3), outer liquid phase tank (4), precise flow rate pumps (57),
multiple emulsion tank (8).
114 Dluska, Markowska-Radomska
nected to a digital camera (Olympus). The multiple emulsions
stability was characterized by backscattering light monitoring
in real time by a Turbiscan Lab and by droplet sizing micro-
scopic observation over time. The drop size was determined by
the imaging software Image Pro Plus 4.5. The rheological be-
havior of multiple emulsions was investigated using a standard
method (Reotest-4.1). To evaluate the efficiency of the ex-
traction process by ELMs, the extracted target solute in the
continuous phase of emulsions was conductometrically
(benzoic acid) analyzed. Likewise, the fraction of active
agent release (salol) was measured spectrophotometrically
in the external phase of emulsions.
3 Results and Discussion
3.1 Influence of Flow Field Conditions on
W
1
/O/W
2
Multiple Emulsion Characteristics
The regimes of multiple emulsion appearance in the CTF
contactor under the examined operating conditions are
presented as a function of axial Reynolds number and Tay-
lor number, as shown in Fig. 2. The key parameters affect-
ing the formation of multiple emulsion in the CTF contac-
tor were the annular gap size, ratio of the phases, and
intensity of the rotational flow. The influence of an axial
flow as a factor that intensifies transport processes is im-
portant as well, especially in the range
of lower rotation rates of the inner cyl-
inder. Multiple emulsions have been
noticed at lower rotation rates with an
increasing axial flow. At smaller rota-
tions, an axial flow influenced drop
diameters more than a rotational one
(Ta <20), as illustrated in Fig. 3. This
confirmed the importance of both flows
for multiple emulsion preparation.
As illustrated in Fig. 3, at higher
rotations of the inner cylinder 24 < Ta
< 28, emulsion drops were still stable
with almost constant diameters. The
ratio of the volumetric flow rates of the
phases has a significant effect on ap-
pearance and yield of multiple emul-
sions under the studied experimental
conditions. Under the operating condi-
tions of this work, multiple emulsions
of the type W
1
/O/W
2
appeared for
fixed ratios of the volumetric flow rates
of the phases inside of each investi-
gated annular gap size (1.5, 2.5, 5 mm).
In the smallest annular gap (1.5 mm),
even under the conditions of relatively
low rotation rates of the internal cylin-
der, it was likely to notice stable multi-
ple emulsions of high volume fraction
of membrane phase drops filled by in-
ternal drops. For the drop size and the
packing of the membrane phase, emul-
sions prepared in an annular gap size of 2.5 mm were compar-
able to those obtained in an annular gap size of 1.5 mm, al-
though they were stable for a shorter period of time. Similarly,
the emulsions characteristic results from similar flow field
conditions of the multiple emulsions appearing in both gaps.
The boundary conditions of multiple emulsion formation in
Chem. Eng. Technol. 2010, 33, No. 1, 113120 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Table 1. Range of the variables of multiple emulsion preparation in the CTF contactor.
Annular gap width of the CTF contactor: d = 1.5, 2.5, 5.0 mm
O
1
/W/O
2
W
1
/O/W
2
Rotational frequency of the inner cylinder
n = 3503860 rpm n = 3502060 rpm
Ratio of the volumetric flow rates of the phases:
Inner/outer = 0.10.8
Membrane/outer = 0.080.25
Ratio of the volumetric flow rates of the phases:
Inner/outer = 0.25
Membrane/outer = 0.250.375
Superficial liquid mixture velocity u:
d = 1.5 mmu = 0.7 10
2
3.7 10
2
m/s
d = 2.5 mmu = 0.4 10
2
2.3 10
2
m/s
d = 5 mmu = 0.2 10
2
1.2 10
2
m/s
Superficial liquid mixture velocity u:
d = 1.5 mmu = 0.9 10
2
3.8 10
2
m/s
d = 2.5 mmu = 0.6 10
2
2.4 10
2
m/s
d = 5 mmu = 0.3 10
2
1.3 10
2
m/s
Table 2. Composition of the multiple emulsions.
W
1
/O/W
2
Inner phase: (0.5 N) NaOH aqueous at 20 C
Membrane phase: isododekan (ShellsolT aliphatic solvent) + Span 83 at 20 C
Outer phase: aqueous solution of Tween 80 at 20 C
O
1
/W/O
2
Inner phase: phenyl salicylate (salol)* as an active agent (drug) in liquid paraffin at 80 C
Membrane phase: gelatin aqueous phase containing 5 % sucrose at 80 C
Outer phase: liquid paraffin at 20 C
*Phenyl salicylate, called salol, has been used as a model hydrophobic reactive agent entrapped in the
internal phase of multiple emulsions. Salol is a white aromatic powder; melting point 42 C. It is
slightly soluble in water; soluble in alcohol, ether, chloroform, and benzene. It is used as an analgesic,
antipyretic, and intestinal antiseptic but in veterinary medicine.
Figure 2. Regimes of single O/W and multiple W
1
/O/W
2
emulsions in
the CTF as correlation of axial Reynolds number and Taylor number.
Multiple Emulsions 115
these both gaps indicated the regime flow of almost overlap-
ping data. As illustrated in Fig. 2, this regime was distinguished
for the rotations Ta to 55 and the liquids mixture velocity Re
ax
to 1.5. The multiple emulsions obtained in the biggest investi-
gated annular gap size (5 mm) were mostly unstable with
much smaller packing. The results showed that preparation of
stable multiple emulsions with optimal characteristics, i.e., a
large enough surface area, required a shear flow created in the
annular gap size of 1.5 mm. Experiments performed with the
emulsion system consisting of an external phase (an aqueous
solution of Tween 80), a membrane phase (an aliphatic sol-
vent: ShellsolT (isododekan) + Span 83), and an internal phase
(NaOH aqueous), allowed to optimize the operating condi-
tions, providing the best characteristics of W
1
/O/W
2
emul-
sions. The mentioned conditions were created in a CTF appa-
ratus with an annular gap size of 1.5 mm for the following
ratios of the volumetric flow rates of the phases: inner/mem-
brane = 1, inner/outer = 0.25, and rotations of the inner cylin-
der: 12501850 rpm [19]. Under these conditions, the average
drop diameters of the membrane phase were in the range of
2641.6 lm and internal phase drops reached the size of
5.611.7 lm, as illustrated in Fig. 3. Exemplary images of
W
1
/O/W
2
emulsions and drop size distribution are presented
in Figs. 4 and 5. The emulsions were characterized by high
packing of the membrane phase drops by the internal phase
drops. The packing volume fraction for the investigated poly-
disperse system of internal drops determined by image analysis
ranged from 0.64 to >0.8. The particle volume fraction at ran-
dom close packing depends on the objects which have to be
packed. When the objects are polydispersed, then the volume
fraction depends on the size distribution and can be arbitrarily
close to 1 [20, 21]. The most suitable ratios of the volumetric
flow rates of the phases for high yield of multiple emulsion
formation in the CTF contactor were: inner/mem-
brane = 1.0 and inner/outer = 0.25. The volume
fraction of the dispersed phases (internal and
membrane) in the whole emulsion of the best
characteristic was 0.33. The optimum content of
surfactants was 2 vol.-% of Tween 80 in an aque-
ous phase and 710 wt % of Span 83 in an organic
phase. The W
1
/O/W
2
emulsions prepared in the
CTF contactor were stable within a storage period
time of 23 days. The backscattering profiles made
with the Turbiscan LAb over the examined time
along the 40 mm cell height of W
1
/O/W
2
emul-
sions showed no marked changes in the character
of profiles. The total intensity of the backscattering
decreased only by about 10% within the examined
period time of 23 days, thereby ensuring no de-
stabilization phenomena. Furthermore, rheological
studies can provide useful information on the mul-
tiple emulsion stability. In this study, the knowl-
edge of rheological data was important in calculat-
ing criteria numbers (Ta, Re).
Fig. 6 shows the apparent viscosities of the best
characteristic W
1
/O/W
2
and O
1
/W/O
2
emulsions.
An apparent viscosity of W
1
/O/W
2
emulsions pre-
pared under shear flow referring to the inner cylinder of CTF
contactor rotations (ranging from 1250 rpm to 1850 rpm) var-
ied from 64 mPas to 57 mPas. The measured flow curves
indicated that the rheological behavior of W
1
/O/W
2
can be de-
scribed as non-Newtonian up to a shear rate of 500 1/s and
nearly Newtonian at higher values of shear rates.
3.2 Influence of Flow Field Conditions on O
1
/W/O
2
Multiple Emulsion Characteristics
The system of immiscible liquids based on cross-linked gelatin
allows to prepare stable multiple emulsions of O
1
/W/O
2
type
with an incorporated reactive agent (drug: salol) in the inter-
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Figure 3. Influence of axial and rotational flow on modal drop diameter of the
membrane and inner phases of W
1
/O/W
2
emulsions formed in the CTF contac-
tor with a gap width of 1.5 mm.
50 m
Figure 4. Multiple emulsion of W
1
/O/W
2
type prepared in the
CTF contactor: n = 1250 rpm, f = 0.33 at u = 0.019 m/s.
116 Dluska, Markowska-Radomska
nal droplets of the organic phase [6]. Exemplary images of
multiple emulsions and drop size distribution are presented in
Figs. 7 and 8.
Fig. 9 shows the flow regimes of O
1
/W/O
2
emulsions in the
CTF contactor. As for W
1
/O/W
2
emulsion formation, the in-
tensity of the rotational flow, the ratio of the phases, and the
gap size are the most important parameters influencing the
O
1
/W/O
2
formation process in the CTF contactor compared
to an axial flow. At a lower rotational frequency of the inner
cylinder the increase in an axial flow caused the appearance of
O
1
/W/O
2
regimes, whereas at higher rotations its action was
not so noticeable. All investigated annular gaps (1.5 mm;
2.5 mm; 5 mm) created flow regimes of multiple emulsions of
various states. The most stable multiple emulsions character-
ized by the highest packing (above 80%) were formed in a
CTF contactor of 1.5 mm gap width under rotational frequen-
cies of the inner cylinder of 18002450 rpm for the ratio of the
phases inner/outer = 0.50.8 and membrane/outer = 0.080.1.
Poor yields of emulsions formed in the gaps of 2.5 mm and
5 mm were observed compared to the smaller gap size of
1.5 mm. The bigger the gap size, the higher rotations are re-
quired to formulate multiple emulsions. This confirmed the
fact of a certain shear stress required to formulate the disper-
sion state of multiple emulsions in the CTF. The internal aver-
age droplet sizes of the best characteristic emulsions were 4
10 lm and of the membrane phase drops 2340 lm [6]. The
volume fraction of the internal phase drops in the membrane
phase drops (the packing volume fraction) determined by im-
age analysis was in the range of 0.36 to >0.8 depending on the
operating conditions in the CTF contactor. The packing of the
membrane phase drops of multiple emulsions increased with
the rotational frequency of the inner cylinder of the CTF con-
tactor increasing up to rotations of about 1800 rpm. Then the
packing volume fraction showed a slight
tendency to be smaller from 0.83 at rota-
tions of 1800 rpm to 0.64 for the rotation
of 2450 rpm. As the rotational frequency
still raised, the packing of the membrane
phase drops decreased to up to 0.36 at ro-
tations of 3800 rpm. The results showed
two-week stable O
1
/W/O
2
emulsions with
remaining constant droplet size through-
out the study period. As shown by mea-
sured profiles of backscattering light, the
drop size distribution of O
1
/W/O
2
emul-
sions was nearly constant during the exam-
ined release time. The O
1
/W/O
2
emulsion
exhibits slight non-Newtonian shear-thin-
ning behavior over the investigated volume
of dispersed phases (0.375), as shown in
Fig. 6. The apparent viscosity of the best
characteristic O
1
/W/O
2
emulsions pre-
pared under shear flow referring to the
inner cylinder of the CTF contactor with
rotations of 1830 rpm and 2330 rpm varied
from 180 mPas to 168 mPas.
Chem. Eng. Technol. 2010, 33, No. 1, 113120 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Figure 5. Drop size distribution of the membrane and inner
phases of W
1
/O/W
2
emulsions.
Figure 6. Apparent viscosity of W
1
/O/W
2
and O
1
/W/O
2
emulsions as a function of shear
stress.
50 m
Figure 7. Multiple emulsion of O
1
/W/O
2
type prepared in
the CTF contactor: n = 1830 rpm, c
s
= 10%, f = 0.375 at u =
0.017 m/s.
Multiple Emulsions 117
4 Some Application Aspects of Multiple
Emulsions Prepared in the CTF
Contactor
4.1 Multiple Emulsions of W
1
/O/W
2
type for
Extraction Process
The best characteristic W
1
/O/W
2
multiple emulsions (large in-
terfacial area for mass transfer) prepared in the CTF contactor
were used as emulsion liquid membranes (ELMs) in a process
of extraction with irreversible chemical reaction. The extrac-
tion by ELMs in the CTF apparatus combines in one step two
processes of the multiple emulsion preparation and extraction.
The experimental apparatus and the procedure of multiple
emulsion preparation were the same as reported in Sections 2
and 3.1. To evaluate the efficiency of the extraction process
by ELMs, the target solute (benzoic acid) was introduced
to the external phase of multiple emulsions. In reference to
this the intensity of rotational flow in the CTF apparatus
on extraction efficiency of the target solute from the exter-
nal aqueous donor phase by ELMs was examined. As the
internal receptor phase aqueous solutions of NaOH were
used. The emulsions W
1
/O/W
2
with a volume fraction of
dispersed phases of 0.33 prepared in the CTF contactor
under rotational frequencies of 12501850 rpm were used
as ELMs. The membrane mass transport without a carrier
agent was investigated. The extraction efficiency by ELMs
in the CTF contactor was calculated based on the changes
of the extracted target solute concentration in the continu-
ous phase of multiple emulsions. In the case of an extrac-
tion process by ELMs it is important to measure the rate
of the leakage of the internal phase (NaOH aq) to the ex-
ternal phase. The volume fraction of the leaked internal
phase was analyzed and considered in the calculation of
extraction efficiency. The experimental results (Tab. 3), ob-
tained for benzoic acid extraction, showed an increase of
extraction efficiency with increasing rotations. The extrac-
tion efficiency of benzoic acid was about 91 % for higher
rotations (1850 rpm) from the investigated range. The ob-
tained results referred to the short time (21 s) which is the
residence time in the continuous apparatus. The batch ex-
traction process usually takes several minutes to remove by
ELM species from the external phase. The results justified
the possibility of using the continuous CTF for a one-step
process with combined multiple emulsion formation and
extraction by ELMs. The shown experimental data are an
example of extraction by ELMs in the CTF contactor for a
model target solute which was benzoic acid. The wider
range investigations of a separation process of organic con-
taminates by ELMs in the CTF contactor are currently pre-
pared for publication.
4.2 Multiple Emulsions of O
1
/W/O
2
type for
Controlled Release of Active Agent
The release rate of an active agent was investigated from
multiple emulsions of O
1
/W/O
2
type depicting four sets of
varying conditions of multiple emulsion preparation in the
CTF contactor (see Sections 2 and 3.2). The release experiments
from the internal paraffin droplets entrapping an active agent
(salol) of O
1
/W/O
2
emulsions were carried out in a stirred tank
at different stirring conditions, namely 100500 rpm. An exam-
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Figure 8. Drop size distribution of the membrane phase and inner
phases of O
1
/W/O
2
emulsions.
Figure 9. Regimes of single W/O and multiple O
1
/W/O
2
emulsions in
the CTF as correlation of axial Reynolds number and Taylor number.
Table 3. Extraction efficiency of benzoic acid by W
1
/O/W
2
multi-
ple emulsions in the CTF contactor.
Rotational frequency
[rpm]
Fraction of NaOH
leakage
Extraction efficiency
[%]
1250 0.044 44.11
1500 0.039 76.38
1850 0.046 91.35
118 Dluska, Markowska-Radomska
ple of release profiles of two sets of multiple emulsions prepared
under different rotational flow in the CTF contactor is pre-
sented in Fig. 10. The release rate of the active agent was found
to be related to the membrane and the internal phase drop sizes
that in turn were dependent on the preparation conditions in
the CTF contactor. The release rate of salol from internal drop-
lets of multiple emulsions prepared at rotations of 1830 rpm
with a salol feed concentration of 10 % is slower than that pre-
pared at 2330 rpm and the same feed concentration. This is due
to the higher interfacial area of the internal drops occupied
membrane phase drops of multiple emulsions of 1830 rpm set
resulting in 94.7 % salol encapsulation efficiency in comparison
to the emulsions of 2330 rpm set having an efficiency of 64.6 %.
The obtained release profiles indicated that a multiple emulsion
formulated in the CTF contactor can be considered for the con-
trol active ingredient delivery.
5 Conclusions
Multiple emulsions as high-value products have a great indus-
trial and medical potential and have been widely applied. The
physical properties (drop size distribution, volume fraction of
internal drops), stability, and rheological behavior of multiple
emulsions determine their application and are tied with the
method of preparation. This paper presents a one-step prepa-
ration method of multiple emulsions in the continuous CTF
contactor in contrast to the conventional two-step procedure.
The proposed method allows to formulate stable multiple
emulsions of W/O/W or W
1
/O/W
2
and O/W/O or O
1
/W/O
2
types depending on the composition of the feeding phases.
Furthermore, the conventional two-step stirring emulsification
method is time-consuming whereas the proposed one-step
method takes much less time, usually several seconds (resi-
dence time). The effect of operating conditions was discussed
to determine flow regimes of the dispersion state of multiple
emulsions in the CTF contactor. The regimes of multiple
emulsion appearance in the CTF contactor under the exam-
ined operating conditions were presented as a function of di-
mensionless numbers (axial Reynolds number and Taylor
number) allowing to determine significant operating parame-
ters. The key parameters affecting multiple emulsion appear-
ance in the continuous CTF contactor were the phase ratio,
the rotational flow, and an annular gap width. The influence of
an axial flow as a factor that intensifies transport processes was
important as well, especially in the range of lower rotation
rates of the inner cylinder related to the state of drop being not
adequately reduced in size. The results showed that stable mul-
tiple emulsions required to apply a defined shear flow. In this
work, all investigated gap sizes (1.5 mm, 2.5 mm, 5 mm) creat-
ed the dispersion state of different structures of the multiple
emulsions. A smaller gap size enabled the shear flow to formu-
late the most stable emulsions of W
1
/O/W
2
and O
1
/W/O
2
types with optimal characteristics, i.e., a large enough surface
area (volume fraction of polydisperse internal drops >80 %).
The paper presents same exemplary data of using multiple
emulsions of type W
1
/O/W
2
as ELMs in the extraction process
with chemical reaction and a type of O
1
/W/O
2
for control ac-
tive agent release. A variety of separation problems involving
the process by an ELM has been investigated over the last three
decades. In the literature there is no data on a method which
combines in one stage two processes: multiple emulsion for-
mation and extraction. In this paper, we proposed the contin-
uous CTF for a one-step method with combined multiple
emulsion formation and extraction by ELMs. The CTF has also
been successfully tested for preparing O
1
/W/O
2
emulsions
entrapping an active substance. The obtained release profiles
were found to be dependent on emulsion characteristics
(structure: drop size and packing) which were in turn depen-
dent on the preparation conditions in the CTF contactor. The
different internal structures of multiple emulsions offer the
possibility of use for control active agent release. The presented
results showed the ability of the CTF apparatus for conducting
processes in multiphase systems.
Symbols used
c
s
[%] feed active agent (salol)
concentration
d [mm] annular gap width of the CTF
contactor
d
m
[lm] mean drop size
n [rpm] rotational frequency of the inner
cylinder
N [%] percentage number content of
drops of diameter d
m
in all
populations
R [m] inner cylinder radius of the CTF
contactor
t [min] time
T [K] temperature
u [ms
1
] superficial liquid mixture velocity
O [] organic phase
W [] aqueous phase
Chem. Eng. Technol. 2010, 33, No. 1, 113120 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.cet-journal.com
Figure 10. Cumulative mass fraction of released agent from O
1
/W/O
2
emulsions vs. time depending on preparation conditions of O
1
/W/O
2
in
the CTF contactor.
Multiple Emulsions 119
Re
ax
[] axial Reynolds number = 2udq
m
/g
Ta [] Taylor number = xR
0.5
d
1.5
q
m
/g
Greek letters
g [Pas] apparent emulsion viscosity
f [] volume fraction of dispersed phases
(membrane and inner) in whole
emulsion
q
m
[kgm
3
] mixture density
x [s
1
] angular velocity
References
[1] A. T. Florence, D. Whitehill, Int. J. Pharm. 1982, 11, 277.
[2] A. Aserin, Multiple Emulsions, Wiley, Hoboken 2007.
[3] M. T. A. Reis, O. M. F. de Freitas, L. M. Ferreira, J. M. R. Car-
valho, J. Membr. Sci. 2006, 269, 161.
[4] S. Sugiura et al., J. Colloid Interface Sci. 2004, 270, 221.
[5] G.-H. Ma, H. Sone, S. Omi, Macromolecules 2004, 37, 2954.
[6] E. Dluska, A. Markowska, Chem. Eng. Process. 2009, 48, 438.
[7] K. Kataoka et al., Chem. Eng. Sci. 1995, 50, 1409.
[8] G. Desmet, H. Verelst, G. Baron, Chem. Eng. Sci. 1996, 51,
1287.
[9] G. Desmet, H. Verelst, G. Baron, Chem. Eng. Sci. 1997, 52,
2383.
[10] C. Nouar, R. Devienne, M. Lebouche, J. Heat Mass Transfer
1987, 30, 639.
[11] S. Wronski, E. Dluska, R. Hubacz, E. Molga, Chem. Eng. Sci.
1999, 54, 2963.
[12] E. Dluska, S. Wronski, R. Hubacz, Chem. Eng. Sci. 2001, 56,
1131.
[13] R. Hubacz, S. Wronski, Exp. Therm. Fluid Sci. 2004, 28, 457.
[14] E. Dluska, J. Wolinski, S. Wronski, Chem. Eng. Technol. 2005,
28, 1016.
[15] R. Hubacz, S. Wronski, Inz. Chem. Proc. (Polish Journal)
2003, 24, 617.
[16] E. Dluska et al., Chem. Eng. Commun. 2007, 194, 1271.
[17] E. Dluska, S. Wronski, T. Ryszczuk, Exp. Therm. Fluid Sci.
2004, 28, 467.
[18] S. Wronski, R. Hubacz, T. Ryszczuk, J. Chem. Eng. 2005, 105,
71.
[19] M. Wolski, M.Sci. Thesis, Warsaw University of Technology
2008.
[20] H. M. Jaeger, S. R. Nagel, Science 1992, 255, 1524.
[21] J. Brujic et al., Faraday Discuss. 2003, 207, 123.
www.cet-journal.com 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Chem. Eng. Technol. 2010, 33, No. 1, 113120
120 Dluska, Markowska-Radomska