Colloids and Surfaces A: Physicochem. Eng.

Aspects 457 (2014) 441448

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

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

Inuences of addition of hydrophilic surfactants on the W/O

emulsions stabilized by lipophilic surfactants
Guojun Lv, Fumin Wang, Wangfeng Cai, Hang Li, Xubin Zhang
School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, PR China

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

O/W/O multiple emulsions were

formed in the emulsion system.
Absorption changes of 1640 cm1 and
3380 cm1 indicate the morphologies
changes.
Micelles transport contributes to the
inversion of W/O to O/W.

a r t i c l e i n f o a b s t r a c t

Article history: Lipophilic surfactants were used in the oil/water system to form W/O emulsions, and the consequences
Received 2 May 2014 of addition of hydrophilic surfactants to the emulsions were examined. The process was monitored by
Received in revised form 8 June 2014 visual and microscopic observations and the droplet size as well as emulsion conductivity were deter-
Accepted 16 June 2014
mined. Multiple oil-in-water-in-oil (O/W/O) emulsions were observed when the hydrophilic surfactants
Available online 20 June 2014
concentrations were low. Surprisingly, the emulsion inverted to oil-in-water (O/W) when the concen-
trations of the hydrophilic surfactants were increased. The infrared (IR) spectrometer was also used to
Keywords:
investigate the interesting phenomenon and the results demonstrated that the absorption changes of
Multiple emulsions
Oil-in-water-in-oil the hydroxyl groups and alkyl groups in IR spectra could effectively explain the morphologies changes.
Phase inversion Morphological evolution of the emulsion with stirring time was applied to analyze the mechanism of the
inversion of W/O to O/W.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Emulsions are kind of dispersions composed of two immiscible
liquids (usually water and organic solvent) that form two phases:
the dispersed phase as liquid droplets and the surrounding contin-
uous phase. Depending on the state of their components, emulsions
can be classied into simple emulsions and multiple emulsions
[1,2]. Multiple emulsions are complex structured uids that the
Corresponding author. Tel.: +86 022789041; fax: +86 022789041.
E-mail address: junguolvtju@163.com (X. Zhang).
droplets of the dispersed phase contain one or several ner droplets
of the continuous phase. Thus, they have also been termed emul-
sions of emulsions. There exist at least two types of multiple
emulsions, namely oil-in-water-in-oil (O/W/O) emulsion, where
oil droplets are located within water droplets that are dispersed
within a continuous oil, and water-in-oil-in-water (W/O/W) emul-
sion, where water droplets are dispersed in oil droplets, which in
turn are dispersed in a continuous aqueous phase. The multiphase,
compartmentalized structure of multiple emulsions makes them
useful in systems requiring controlled release or uptake capabili-
ties. Research in multiple emulsions has experienced a continuous
increase in the last years, as evidenced by the numerous publica-
tions [36]. This enormous interest is triggered by the widespread

http://dx.doi.org/10.1016/j.colsurfa.2014.06.031
0927-7757/ 2014 Elsevier B.V. All rights reserved.
442 G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 441448
applications, for example, food [7], cosmetic [8], polymer synthesis
[9] and pharmacy [10,11].
Multiple emulsions are typically more difcult to prepare and
control than simple emulsions, in large part given the presence
of two thermodynamically unstable interfaces, i.e. the W/O inter-
face and the O/W interface. Consequently, a systematic study of
the effects of composition parameters and different processes such
as (i) type of the oil phase, (ii) phase volume fraction, (iii) type of
emulsifying agents, (iv) hydrophilic/lipophilic surfactant ratio, and
(v) process variables (agitation speed and emulsication tempera-
ture) on emulsion formation and stability is necessary if multiple
emulsion formation is considered. Moreover, such a systematic
investigation will contribute not only to our understanding of mul-
tiple emulsions, but also emulsion systems in general, from both a
practical and theoretical view [12].
In the case of O/W/O emulsions, a two-step method [13,14] is
generally adopted where an O/W emulsion is formed, and then
dispersed in a secondary oil phase. The primary emulsion (O/W)
is typically made using a hydrophilic surfactant with a high HLB
whereas in the second step, the primary emulsion is gently emul-
sied within an external phase that contains a lipophilic surfactant
with a low HLB to produce the O/W/O emulsions. Moreover, the
primary O/W emulsion is carried out under high-shear conditions
to obtain small droplets while the secondary emulsication step
is prepared with less shear force to avoid rupture of the internal
droplets. The composition of the multiple emulsion is of signif-
icant importance to the stability and release properties. Much
work has been carried out on optimizing the nature of the sur-
factants, the nature of the oils, and the volume fractions of the
water and the oil [15]. Besides, the microcapillary device [16] and
membranes [17] were utilized to the O/W/O multiple emulsion
formation.
In this study, the W/O emulsions stabilized by lipophilic sur-
factants were prepared at room temperature. Then appropriate
amount of hydrophilic surfactants were added into the system and
the consequences of addition of hydrophilic surfactants were sys-
tematically studied. The obtained emulsions were characterized by
visual and microscopic observations and the droplet size as well as
emulsion conductivity were determined.
2. Materials and methods
2.1. Materials
Liquid parafn (d = 0.860.89 g/cm3 , C.P.) is used as the oil phase
and its purity is greater than 99%. The components of the liq-
uid parafn are mainly isoalkane, and the carbon number ranges
from 16 to 26. The water phase is deionized water containing
0.2% (w/w) potassium chloride (99.5%, C.P.) to set the electrical
conductivity. The lipophilic surfactants are Sorbitan monopalmi-
tate (Span 40, HLB = 6.7, C.P.), sorbitan monoctadecanoate (Span
60, HLB = 4.7, C.P.) and sorbitan monooleate (Span 80, HLB = 4.3,
C.P.). The hydrophilic surfactants are polyoxyethylene sorbitan
monolaurate (Tween 20, HLB = 16.7, C.P.), polyoxyethylene sorbi-
tan monopalmitate (Tween 40, HLB = 16.0, C.P.), polyoxyethylene
sorbitan monooleate (Tween 80, HLB = 15.0, C.P.), polyoxyethy-
lene (10) nonylphenol (OP-10, HLB = 14.8, C.P.) and sodium dodecyl
sulfate (SDS, HLB = 40.0, C.P.). All reagents are purchased from
Shanghai Civi Chemical Technology Co., China and used as received
without further purication.
The concentrations of water (oil) are expressed as percent (v/v)
based on the volume of the water (oil) present in the systems as
100 vol%; the hydrophilic surfactants concentrations are expressed
as millimole (mM).
2.2. Preparation of emulsions
The primary W/O emulsions were prepared rst and then
hydrophilic surfactants were added into the W/O emulsion in order
to investigate the inuences. The primary W/O emulsions were pre-
pared by adding the aqueous phase (50%) containing 0.2% (w/w)
KCl solution to the oil phase with 2 wt% lipophilic surfactants
included. After adding the water phase to the oil phase, the emul-
sions were homogenized using a homogenizer (AD200l-P, Shanghai
Angni Instruments & Meters Co., Ltd.) for 30 min at 4000 rpm. Then
the hydrophilic surfactants were added into the emulsions and the
experimental parameters were maintained constant at a stirring
rate of 4000 rpm for 20 min. After the emulsication, the conductiv-
ities and IR spectra of the samples were immediately determined,
and then the samples were poured into glass tubes and carefully
sealed.
The emulsion conductivity was immediately observed by a DDS-
307 conductometer (Shanghai Precision & Scientic Instrument Co.,
Ltd.) after stirring with a Pt/platinized electrode at 25 C. Large
conductivity values indicate O/W emulsions, whereas low val-
ues indicate W/O emulsions. At the same time, IR spectra were
monitored by a Fourier transform infrared (FTIR) spectroscopy
(TENSOR27, Germany Brooke Fourier Infrared Spectrometer Co.,
Ltd.). Software collected spectra in absorbance mode (wavenum-
bers from 4000 to 400 cm1 ) and this spectral range provided
obvious changes of hydroxyl groups and alkyl groups. A high speed
CCD camera (AOS X-PRI) was used to observe emulsion morpholo-
gies. For sample preparation, a small amount of the emulsion was
placed on the microscope glass slide and then quickly covered by
the cover slip and the covered sample was nger pressed to make
it as thin as possible. The droplet sizes were determined by Photon
correlation spectroscopy (PCS) using Malvern Mastersizer 3000. An
argon laser with variable intensity was used to cover the size range
involved. Measurement was carried out at 25 C with a scattering
angle of 90 . Intensity averaged radius were computed from the
intensity autocorrelation data with the cumulants method. And the
intensity-intensity time correlation functions were analyzed by the
CONTIN method. Before the measurement, the O/W samples were
diluted with water which O/W/O samples were diluted with octane.
Note that for kinetically stabilized emulsions, dilution does not alter
the original emulsion drop size.
3. Results and discussion
3.1. Development of the primary W/O emulsions
The instability of multiple emulsions can be increased by the use
of unsaturated oils in the oil phase, which prevents a close packed,
condensed interfacial lm [18,19]. Schmidts et al. [20] reported that
parafn oils, particularly the heavy parafn, formed more stable
formulations. Thus, heavy parafn and three lipophilic surfactants
with HLB values ranging from 4.3 to 6.7 were chosen for the prepa-
ration of primary W/O emulsions. The surfactants are of the same
surfactant class (sorbitan ester) with different side chains resulting
in various HLB values. It was found that the most stable emul-
sion was obtained using heavy parafn stabilized with Sorbitan
monooleate. Fig. 1 shows an optical micrograph of water-in-oil
(50%, v/v water) emulsion. The conductivity of the emulsion is
relative low (1 S/cm), indicating the continuous oil phase. The
viscosity of this primary emulsion was 1.5 Pa s and the average
water droplet size was approximately 0.5 m. Moreover, the emul-
sion remained stable for at least 2 days with no measurable change
in droplet size distribution. The rHLB of parafn oil is about 4 [21]
and consequently emulsiers with an HLB of approximately 4 will
create the most stable formulations.
 G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 441448
Fig. 1. Optical micrograph of water-in-oil emulsion stabilized by Span 80 imaged
after 1 week after formation. Bar equals to 25 m.
3.2. Characterization of O/W/O multiple emulsions
In this section, Tween 20 and OP-10 were added into the Span
80-stabilized emulsions and the consequences were systematically
studied. For Tween 20, a threshold concentration of 3 mM has to
be exceeded before we notice any impact. At concentrations below
the threshold, addition of Tween 20 shows no obvious changes
to the emulsion conductivity (see Fig. 2) and bottle tests (see
Fig. 3). The emulsions are O/W/O (see Fig. 4(a)) and oil continuous,
contributing to the low emulsion conductivity. Conductivity mea-
surements are commonly used for evaluating the nature of multiple
emulsions [22,3]. For 3 mM Tween 20, the emulsion separates into
three layers, one being an upper layer with a high concentration
of the oil phase, the next layer is similar to the original emulsion
and the lower one with a high concentration of the water phase.
When the system presents a three-phase behavior under stirring,
a phase separation occurs between middle phase and water/oil
excess phases, increasing the number of possible emulsion mor-
phologies considerably. As the concentrations of Tween 20 are
increased further, the aqueous phase becomes continuous phase
(see Fig. 4(b)) and the O/W emulsions are obtained. The emulsions
have large conductivities (see Fig. 2) and cream (see Fig. 3).
For OP-10, the low conductivity values occurred till OP-10 con-
centration exceeded 5 mM. When 1 mM OP-10 was added, the
Fig. 2. Experimental conductivities immediately observed after stirring versus the
addition of Tween 20 and OP-10 to the Span 80-stabilized emulsions.
443
Fig. 3. Digital photographs of the Span 80-stabilized emulsions with the addition
of Tween 20, taken 1 week after preparation.
obtained emulsion was still W/O, which sediment, releasing a clear
oil phase above time. For 2 to 4 mM OP-10, the emulsions inverted
into O/W/O (see Fig. 4(c)) and the emulsion conductivity was still
low less than 1 S/cm, separating into three layers when rested in
bottle tests for 1 week. For 5 mM OP-10 or more, O/W emulsions
(see Fig. 4(d)) were obtained and have large emulsion conductivity.
As the particle sizes of the emulsion droplets are the cru-
cial parameter in dening their application and stability, all the
prepared emulsions are carefully characterized in terms of their
particle diameter. It is found that particle diameter was notably
affected by HLBmix calculated according to the following relation-
ship.
HLBmix = HLBA A% + HLBB B%
where HLBmix is the HLB value of the surfactants combination,
HLBA/B is the HLB value of surfactant A and B, and A% and B% repre-
sent the weight percentages of A and B, respectively.
This is illustrated in Fig. 5 showing example of the relationship
between HLBmix and the particle diameter determined immedi-
ately after their preparation. As it can be seen, the particle size
of emulsions was, in general, growing with an increasing HLBmix .
Upon addition of Tween 20 and OP-10, the HLBmix of the emulsion
system increased and more and more oil droplets were included
inside the water phase, thus increasing the multiple emulsion drop
size. As expected, at low HLBmix (low concentration of both Tween
20 and OP-10), the oil-in-water droplets remained stable and
exhibited no coalescence over the 6 h observation period. As HLBmix
were increased (increasing the concentrations of Tween 20 and
OP-10), the destabilizing effect became observable. The increase
of particle size with HLBmix contributed to the enhancement of
coalescence effect of O/W/O droplets and the nal transition.
3.3. Phase inversion in the emulsion system
Multiple emulsions have potential for many applications. How-
ever, multiple emulsions are, in the main, extremely unstable. Two
processes in particular must be borne in mind when it comes to
multiple emulsion destabilization: multiple drop break-down and
coagulation of multiple droplets. Previous studies have shown that
the composition of multiple emulsions, especially the selection of
appropriate emulsiers, plays a major role in terms of producing
stable formulations [6]. Jiao et al. [23] demonstrated that the ratio
of hydrophilic and lipophilic surfactants signicantly affected the
444 G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 441448

Fig. 4. Optical micrographs of addition of the hydrophilic surfactants to the Span 80-stabilized emulsions: (a) 3 mM Tween 20, (b) 4 mM Tween 20, (c) 4 mM OP-10 and (d)
5 mM OP-10. Bar equals to 25 m.

multiple emulsion stability. Thus, the hydrophilic surfactants con- to the Span 60-stabilized emulsion. The Tween 20 concentration
centrations on the O/W/O multiple emulsion stability were studied needed for the inversion of the Span 40-stabilized emulsion was
and the inversion results were displayed in Table 1. only 0.5 mM. Based on the mentioned results, it was found that
For Span 80-stabilized emulsions, the inversion of W/O to O/W the more stable primary W/O emulsion, the more stable O/W/O
do not happen with addition of Tween 40 and Tween 80 even at emulsion and the more difcult phase inversion occur. Corre-
high concentrations to the Span 80-stabilized emulsions. It was sponding results, namely the decrease of critical concentration
observed that gel emulsions were formed and photographs of gel for the inversions in the W/O emulsions stabilized by Span 80,
emulsions were shown in Fig. 6. Gelling is a generic evolution that Span 60 and Span 40 were also observed in other four hydrophilic
may occur over a wide variety of conditions and it may be produced surfactants.
by application of an intense shear or upon centrifugation [2426]. IR spectrum is one of the classical methods for structure deter-
Gelling of the emulsions can be induced by the so-called partial mination due to its sensitivity to the chemical composition and
coalescence phenomenon [27], which contributes to formation of architecture of molecules. Zhao et al. [30] demonstrated that
a 3D rigid network of interconnected droplets. This scenario occurs the enhancement of the absorption bands due to the hydroxyl
preferentially when the average droplet size is large [28]. Crys- groups conrmed the modication of the TiO2 nanoparticles
tals are believed to orientate toward the oil/water interface and
when such crystals are present within the thin lm separating two
droplets, they may penetrate the lm and bridge the surfaces, caus-
ing the droplets to coalesce. If the crystallized fraction within the
globules is sufcient, the intrinsic rigidity restrains relaxation to
the spherical shape driven by surface tension after each coales-
cence event. As time passed by, large stress bearing clusters appear
and grow by the accretion of any other primary droplet or clus-
ter until a rigid network made of partially coalesced droplet is
formed, in which the original droplet shape remains recognizable
[29].
For Span 80-stabilized emulsion, phase inversion was observed
till Tween 20 concentration exceeded 4 mM. However, the inver-
sion of W/O to O/W was observed when 3.5 mM Tween 20 added

Table 1
Phase inversion in the emulsion system.

Tween 20 Tween 40 Tween 80 OP-10 SDS

Span 40

Span 60

Span 80
Fig. 5. Droplet size as a function of HLBmix .
 G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 441448 445

Fig. 6. Digital photographs of addition of the hydrophilic surfactants to the Span 80-stabilized emulsions: 15 mM Tween 40 ((a) and (b)), 30 mM Tween 80 ((c) and (d)).

and the inversion of TiO2 nanoparticle stabilized emulsions. An

increase in intensity of the hydroxyl stretching absorption in FTIR
spectra veried the phenomena of water absorbing in the drywet
phase inversion [31]. The infrared spectra of the emulsions with
the addition of Tween 20 and OP-10 were recorded in Fig. 7 and
compared to analyze the phase inversions. For 3 mM Tween 20,
the emulsions are O/W/O and oil continuous phase, contributing
to weak absorption bands in the 1640 cm1 and 3380 cm1 . The
adsorbed bands show strong absorbance at 2920 cm1 , 2850 cm1
and 1458 cm1 due to the stretching vibration and bending vibra-
tion of alkyl groups (CH3 and CH2 ) from parafn oil. When Tween 20
concentration is increased to 4 mM, the emulsions invert into O/W
and water continuous phase. Thus, the absorption bands due to the
hydroxyl groups from H2 O were greatly strengthened whereas the
absorption bands of alkyl groups were greatly weaken. For OP-10,
the saltation of IR spectrum occurred at about 5 mM, which cor-
responded to the conductivities changes. The obtained IR spectra
showed a clear shift between the two normal morphologies, which
agreed with micrographs changes.
IR spectra of 5 mM Tween 20 and 6 mM OP-10 to the Span 80-
stabilized emulsion were collected during the inversion route. Fig. 8
shows the progressive shift of the spectra baseline during inversion
process. Phase inversion of W/O to O/W caused the enhance-
ment of absorption of the hydroxyl groups and the reduction of
absorption of the alkyl groups. The absorbance around 1640 cm1
and 3380 cm1 showed the most reproducible results during the
emulsion inversion, and it was chosen to compare IR spectra and
conductivity results (Fig. 9). It is worth note that the IR spectrum is
able of detecting emulsion phase transition between the O/W and
W/O types of morphologies.
The emulsion inversion presented an intermediary conductiv-
ity and IR spectra baseline shift between the two normal emulsion
morphologies (W/O and O/W) in the transition region (labeled in
Fig. 9). In general, O/W emulsion has high conductivity whereas
the conductivity of W/O emulsion is relative low (1 S/cm). Pre-
liminary, the conductivities of the emulsion system are at low
values, indicating the continuous phase is the oil phase and the
emulsions are W/O. When 5 mM Tween 20 and 6 mM OP-10 are Fig. 7. Infrared spectra of the Span 80-stabilized emulsions with the addition of
added, the conductivities increase to high values, which indicates Tween 20 (a) and OP-10 (b).
446 G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 441448
Fig. 8. IR spectra for emulsion inversions of 5 mM Tween 20 (a) and 6 mM OP-
10 (b) to the Span 80-stabilized emulsions. Continuous lines for W/O and O/W.
Transmittances of transition region are shown in dashed lines.
O/W emulsions are obtained and the water phase is the continu-
ous phase. Moreover, the changes of the absorption of 1640 cm1
and 3380 cm1 corresponded to the phase inversion observed in
conductivities changes. In this validation diagram, there is an evi-
dent correlation between measurements.
For the abnormal-to-normal emulsion inversion triggered by
continuous stirring, much work reported that the inversion takes
place through the formation of a multiple emulsion in which
the external phase is continuously included as droplets inside
the original dispersed phase drops [32,33]. The images shown
in Fig. 10 illustrate the inversion of the emulsion morphologies.
At the beginning of stirring, the emulsion was W/O. With the
increase of stirring time, O/W/O multiple emulsions gradually
occurred and more and more oil phase was included as small
oil droplets inside the water phase, thus increasing the multiple
emulsion drop size (see Fig. 10(a)(c)). When the stirring time
exceeded 3 min, the emulsion morphology inverted into O/W (see
Fig. 10(d)) and the emulsion conductivity reached a maximum
value of 34.5 S/cm (see Fig. 9(a)). For OP-10, the maximum con-
ductivity value 61.2 S/cm was reached and the O/W emulsion
was obtained when the stirring time exceeded 4 min. Based on the
results mentioned above, we consider that the emulsion inversion
of W/O to O/W is triggered through the formation of an intermedi-
ate O/W/O multiple emulsion.
Fig. 9. IRs validation for the inversions of 5 mM Tween 20 (a) and 6 mM OP-10 to
the Span 80-stabilized emulsions are compared using transmittances obtained by
IR spectroscopy and conductivity measures.
3.4. Mechanism of the phase inversions
Multiple water-in-oil-in-water emulsions were formed by addi-
tion of Tween 20 and OP-10 to Span 80-stabilized emulsions.
This indicates that the formation of O/W/O multiple emulsions via
adding hydrophilic surfactants to the W/O emulsions stabilized by
lipophilic surfactants may be a general phenomenon.
The surfactant Span 80 is generally regarded as a lipophilic
molecule, with HLB value of 4.3. According to Bancroft rule, the
preferred external phase of an emulsion is the one in which the
surfactant is more soluble, a W/O emulsion is favored by the emul-
sication of Span 80 in the water/oil system. It is well known that
the most important role of emulsiers during emulsication is to
adsorb at the water/oil interface and lower the interfacial tension.
Besides, the emulsiers will also exist in the oil continuous phase
in the form of micelle and monomer if the concentration is high
enough. In the present work, the addition of the oil-soluble emul-
sier Span 80 is much larger than its cmc (0.43 mM according to
Ref. [34]). Thus, there is a large amount of reversed micelles in the
oil phase ((a) in Scheme 1). Reversed micelles (RMs) are thermo-
dynamically stable isotropic dispersions consisting of water in oil
solubilized by an interfacial lm of surfactant. They are aggregates
of surfactant molecules with their polar groups concentrated in the
interior of the aggregate with their hydrophobic moieties extended
into and are surrounded by the bulk apolar solvent. Due to their
unique ability to solubilize water in organic solvents in the presence
 G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 441448 447

Fig. 10. Morphological evolution of 5 mM Tween 20 added into 2 wt% Span 80-stabilized emulsion with stirring time: (a) 0.5 min, (b) 1.0 min, (c) 2 min and (d) 3 min. Bar
equals to 25 m.

Scheme 1. Schematic illustration for the W/O O/W/O O/W emulsion transition.

of surfactants, reversed micelle system has attracted the attention
of research workers from various elds of science and technology
[35,36].
Tween 20 is a hydrophilic nonionic surfactant with a
hydrophilelipophile balance value of 16.7 and a critical micelle
concentration (cmc) value of 0.02 mM [37] in parafn oil. When
1 mM Tween 20 was added into the W/O emulsion, HLBmix of the
emulsion system increased to 11.1 and W/O emulsion was unstable.
Thus, mixed micelles are formed in oil continuous phase and the
oil solubilization of mixed micelles will transfer the oil molecules
into water droplets. Subsequently, a multiple O/W/O emulsion in
which the inner O/W emulsion droplet is formed ((b) in Scheme 1).
The droplet coalescence is inuenced by the collision between the
droplets, which is a function of the droplet size and dynamics of
the dispersion. For coalescence to occur, the droplets must rst
collide and remain in contact long enough for the intervening liq-
uid lm to drain to its critical thickness, which upon lm rupture
occurs [38]. As the Tween 20 concentration approaches 4 mM, the
HLBmix approached critical value 14.0 and the larger inner O/W
droplets were observed and this induces more coalescence among
the droplets, which results in a rapidly increasing droplet diameter.
Subsequently, the multiple emulsions invert to O/W emulsion ((c)
in Scheme 1), indicating emulsion inversion take place.
4. Conclusions
In this study the effects of the addition of hydrophilic surfactants
on the water-in-oil (W/O) emulsions stabilized by lipophilic sur-
factants were studied. Conductivity measurement, bottle test and
microscopic observations were used as indicators to investigate the
effects in the process. Upon the addition of hydrophilic surfactants,
O/W/O multiple emulsions were initially obtained, and inverted
to O/W emulsion at high concentration. The different absorbed
infrared radiations of 1640 cm1 and 3380 cm1 in IR spectra can
448 G. Lv et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 457 (2014) 441448
effectively explain the two normal morphologies changes. The vali-
dation was performed by comparing results obtained with IR to
those with conductometry. Moreover, the mechanism of the emul-
sion inversion is that micelle transport causes the formation of an
intermediate O/W/O multiple emulsion, which leads to the nal
inversion.
Acknowledgements
We gratefully acknowledge the nancial support by the National
Basic Research Program of China (973 Program) (Grant No.
2012CB720302) and Program for Changjiang Scholars and Innova-
tive Research Terms in Universities (IRT0936).
References
[1] C.X. Zhao, A.P.J. Middelberg, Microuidic mass-transfer control for the simple
formation of complex multiple emulsions, Angew. Chem. Int. Ed. 121 (2009)
73447347.
[2] B.P. Binks, J.A. Rodrigues, Inuence of surfactant structure on the double inver-
sion of emulsions in the presence of nanoparticles, Colloids Surf. A 345 (2009)
195201.
[3] J.S. Li, J.L. Zhang, B.X. Han, Y.J. Zhao, G.Y. Yang, Formation of multiple water-in-
ionic liquid-in-water emulsions, J. Colloid Interface Sci. 368 (2012) 395399.
[4] L. Besnard, F. Marchal, J.F. Paredes, J. Daillant, N. Pantoustier, P. Perrn, P. Gue-
noun, Multiple emulsions controlled by stimuli-responsive polymers, Adv.
Mater. 25 (2013) 28442848.
[5] A. Schuch, P. Deiters, J. Henne, K. Khler, H.P. Schuchmann, Production
of W/O/W (water-in-oil-in-water) multiple emulsions: droplet breakup and
release of water, J. Colloid Interface Sci. 402 (2013) 157164.
[6] T. Schmidts, D. Dobler, C. Nissing, F. Runkel, Inuence of hydrophilic surfactants
on the properties of multiple W/O/W emulsions, J. Colloid Interface Sci. 338
(2009) 184192.
[7] R. Lutz, A. Aserin, L. Wicker, N. Garti, Double emulsions stabilized by a charged
complex of modied pectin and whey protein isolate, Colloids Surf. B 72 (2009)
121127.
[8] K. Miyazawa, I. Yajima, I. Kaneda, T. Yanaki, Preparation of a new soft capsule
for cosmetics, J. Cosmet. Sci. 51 (2000) 239252.
[9] N. Rizkalla, C. Range, F.X. Lacasse, P. Hildgen, Effect of various formulation
parameters on the properties of polymeric nanoparticles prepared by multiple
emulsion method, J. Microencapsul. 23 (2006) 3957.
[10] W. Liu, X.L. Yang, W.S. Winston Ho, Preparation of uniform-sized multiple
emulsions and micro/nano particulates for drug delivery by membrane emul-
sication, J. Pharm. Sci. 100 (2011) 7593.
[11] A. Djedour, F. Boury, J.L. Grossiord, Modulation of the release from a W/O/W
multiple emulsion by controlling the viscoelastic properties of the two inter-
faces, J. Durg Deliv. Sci. Technol. 19 (2009) 197203.
[12] J.M. Lee, K.H. Lim, D.H. Smith, Formation of two-phase multiple emulsions
by inclusion of continuous phase into dispersed phase, Langmuir 18 (2002)
73347340.
[13] Y.J. Hwang, C. Oh, S.G. Oh, Controlled release of retinol from silica particles
prepared in O/W/O emulsion: the effects of surfactants and polymers, J. Control.
Release 106 (2005) 339349.
[14] Y.H. Cho, J. Park, Evaluation of process parameters in the O/W/O multiple emul-
sion method for avor encapsulation, J. Food Sci. 68 (2003) 53538.
[15] A. Benichou, A. Aserin, N. Garti, O/W/O double emulsions stabilized with
WPIpolysaccharide conjugates, Colloids Surf. A 297 (2007) 211220.
[16] A.R. Abate, D.A. Weitz, High-order multiple emulsions formed in
poly(dimethylsiloxane) microuidics, Small 5 (2009) 20302032.
[17] G.T. Vladisavljevic, R.A. Williams, Recent developments in manufacturing
emulsions and particulate products using membranes, Adv. Colloid Interface
Sci. 113 (2005) 120.
[18] M.S. Lobo, M.S. Kislalioglu, Effect of unsaturation of C18 fatty acids at liquid
parafnwater interfaces, J. Dispers. Sci. Technol. 20 (1999) 783794.
[19] T.V. Vasudevan, M.S. Naser, Some aspects of stability of multiple emulsions in
personal cleansing system, J. Colloid Interface Sci. 256 (2002) 208215.
[20] T. Schmidts, D. Dobler, A.C. Guldan, N. Paulus, F. Runkle, Multiple W/O/W emul-
sions using the required HLB for emulsier evaluation, Colloids Surf. A 372
(2010) 4854.
[21] W.C. Grifn, Classication of surface active-agents by HLB, J. Soc. Cosmet. Chem.
1 (1949) 311326.
[22] F. Bouchama, G.A. van Aken, A.J.E. Autin, G.J.M. Koper, On the mechanism of
catastrophic phase inversion in emulsions, Colloids Surf. A 231 (2003) 1117.
[23] J. Jiao, D.J. Burgess, Rheology and stability of water-in-oil-in-water multi-
ple emulsions containing Span 83 and Tween 80, AAPS PharmSci 5 (2003)
6271.
[24] E. Davies, E. Dickinson, R. Bee, Shear stability of sodium caseinate emul-
sions containing monoglyceride and triglyceride crystals, Food Hydrocolloid
14 (2000) 145153.
[25] G.A. van Aken, Aeration of emulsions by whipping, Colloids Surf. A 190 (2001)
333354.
[26] K. Golemanov, S. Tcholakova, N.D. Denkov, T. Gurko, Selection of surfactants
for stable parafn-in-water dispersions, undergoing solid-liquid transition of
the dispersed particles, Langmuir 22 (2006) 35603569.
[27] K. Boode, P. Walstra, Partial coalescence in oil-in-water emulsions. 1. Nature of
the aggregation, Colloids Surf. A 81 (1993) 121158.
[28] J. Giermanska, F. Thivilliers, R. Backov, V. Schmitt, Gelling of oil-in-water emul-
sions comprising crystallized droplets, Langmuir 23 (2007) 47924799.
[29] V. Uskokovic, M. Drofenik, Reverse micelles: inert nano-reactors or physico-
chemically active guides of the capped reactions, Adv. Colloid Interface Sci.
133 (2007) 2334.
[30] G.J. Lv, F.M. Wang, W.F. Cai, X.B. Zhang, Characterization of the emulsions
formed by catastrophic phase inversion, Colloids Surf. A 450 (2014) 141147.
[31] Z.H. Zhao, W.X. Liu, Z.Y. Liu, P.X. Ding, H.D. Li, Phase inversion of TiO2 nanoparti-
cle stabilized emulsions of alkenyl succinic anhydride, Chem. Eng. Sci. 87 (2013)
246257.
[32] G.J. Lv, F.M. Wang, W.F. Cai, X.B. Zhang, Characterization of the addition of
lipophilic Span80 to the hydrophilic Tween 80-stabilized emulsions, Colloids
Surf. A 447 (2014) 813.
[33] M. Rondn-Gonzlez, L.F. Madariaga, V. Sadtler, L. Choplin, J.-L. Salager, Emul-
sion catastrophic inversion from abnormal to normal morphology. 8. Effect of
formation on the inversion produced by continuous stirring, Ind. Eng. Chem.
Res. 48 (2009) 29132919.
[34] E. Santini, L. Liggieri, L. Sacca, D. Clausse, F. Ravera, Interfacial rheology
of Span 80 adsorbed layers at parafn oil-water interface and correlation
with the corresponding emulsion properties, Colloids Surf. A 309 (2007)
270279.
[35] B.K. Paul, R.K. Mitra, Water solubilization capacity of mixed reverse micelles:
effect of surfactant component, the nature of the oil, and electrolyte concen-
tration, J. Colloid Interface Sci. 288 (2005) 261279.
[36] D.E. Rosenfeld, C.A. Schmuttenmaer, Dynamics of the water hydrogen bond net-
work at ionic, nonionic, and hydrophobic interfaces in nanopores and reverse
micelles, J. Phys. Chem. B 115 (2011) 10211031.
[37] B.J. Shiau, D.A. Sabatini, J.H. Harwell, Properties of food grade (edible) surfac-
tants affecting subsurface remediation of chlorinated solvents, Environ. Sci.
Technol. 29 (1995) 29292935.
[38] V. Schmitt, C. Cattelet, F. Leal-Calderon, Coarsening of alkane-in-water emul-
sions stabilized by nonionic poly(oxyethylene) surfactants: The role of
molecular permeation and coalescence, Langmuir 20 (2004) 4652.