Colloids and Surfaces A: Physicochem. Eng.

Aspects 385 (2011) 126–133

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

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

Synthesis of temperature-responsive hybrid capsules and their controlled

release property
Mian Wang a , Kui Zhang a , Wei Wu a,∗ , Jianfeng Chen a,b , Pengyuan Zhang b,∗∗
a
State Key Laboratory of Organic Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
b
Research Center of the Ministry of Education for High Gravity Engineering, Technology, Beijing University of Chemical Technology, Beijing 100029, China

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

Article history: In this work, a temperature-responsive hybrid capsules (TRHCs) was prepared from inverse pickering
Received 14 February 2011 emulsion polymerization route. The aqueous solution of N-isopropyl acrylamide and poly (N-isopropyl
Received in revised form 29 May 2011 acrylamide) was emulsified into an oil phase containing divinyl benzene (DVB) by sonication to obtain
Accepted 31 May 2011
a water-in-oil (W/O) pickering emulsion stabilized by modified silica nanoparticles. Then the emulsion
Available online 12 June 2011
was polymerized to obtain the hybrid capsules. The sizes of the capsules are about 5–10 ␮m and can be
tuned by the modified silica nanoparticles concentration in continuous phase. The capsules wall consists
Keywords:
of two layers: a solid particle layer and a polymer layer, whose thickness can be conveniently controlled
Pickering emulsion
Temperature-responsive
by adjusting the DVB concentrations in the continuous phase before polymerization. The as-synthesized
Hybrid capsules capsules exhibit good temperature-responsive property with a phase-transition temperature of 27 ◦ C.
Controlled release The controlled release experiment shows that the release rate of a model drug (Rhodamine B) from the
hybrid capsules can be controlled by adjusting the temperature of the release medium. When the medium
temperatures were 25 ◦ C and 45 ◦ C, the released percents of Rhodamine B from TRHCs within 35 h were
25.7% and 70.9%, respectively.
© 2011 Elsevier B.V. All rights reserved.

1. Introduction like organic–inorganic hybrid microspheres by adding auxiliary

Microcapsules with a well-defined structure have attracted
more and more interest because they have many potential appli-
cations, such as delivery systems (for drugs, cosmetics, dyes,
inks, etc.), encapsulation, confined-space catalysis and separa-
tion [1–4]. A variety of chemical and physicochemical methods
have been reported for the preparation of hollow materials [5–7].
Recently, pickering emulsions stabilized by solid particles have
attracted extensive attention. Pickering emulsion polymerization
can be employed as a facile approach to design hollow cap-
sules and core–shell structured composite spheres [8–12]. Not
only are these emulsions often more stable than their surfactant-
stabilized analogues, but also the emulsion droplets can serve
as templates guiding the assembly process of the solid parti-
cles onto their interfaces, which might find numerous potential
or practical applications [13–17]. For example, Armes and co-
workers [18,19] and Chen et al. [20,21] applied nano silica particles
as “Pickering emulsifier” and successfully prepared raspberry-
∗ Corresponding author. Tel.: +86 10 64443134; fax: +86 10 64434784.
∗∗ Corresponding author. Tel.: +86 10 64449453; fax: +86 10 64449453.
E-mail addresses: wuwei@mail.buct.edu.cn (W. Wu), zhangpy@mail.buct.edu.cn
(P. Zhang).
monomers. Voorn et al. [10] prepared polymer clay nanocompos-
ite latex particles by inverse pickering emulsion polymerization
stabilized with hydrophobic montmorillonite platelets.
The stimuli-sensitive polymer is generally defined as a smart
polymer, which exhibits a drastic change in its properties, respond-
ing to small variations in physical or chemical stimuli, such as
pH, temperature, and ionic species. These characteristics make the
materials especially suitable for applications in medical and biolog-
ical fields, such as controlled drug release and protein separation,
and being studied extensively [22–26].
Our group had synthesized poly(N-isopropylacrylamide)/
poly(methyl methacrylate)/silica hybrid capsules via inverse pick-
ering suspension polymerization using silica particles as stabilizers
[27]. However, the thermo-sensitivity of the capsules is not obvi-
ous due to the effect of the outer monomer methyl methacrylate
(MMA) and the unpolymerized temperature-sensitive monomers.
In this work, we used an aqueous solution of N-isopropylacrylamide
(NIPAM) and poly (N-isopropyl acrylamide) (PNIPAM) as the aque-
ous phase and liquid paraffin containing divinyl benzene (DVB) as
the oil phase in order to improve the thermosensitivity of the hybrid
capsules. The capsule consisting of two layers, a solid particle layer
and a polymer layer, was synthesized successfully. The effects of
particle concentration, PNIPAM concentration, and DVB concen-
tration on the preparation of hybrid capsules were discussed. The

0927-7757/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2011.05.058
 M. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 385 (2011) 126–133 127

improved thermal-sensitive and controllable release properties of

the as-synthesized capsules were also investigated.

2. Experimental

2.1. Materials

N-isopropylacrylamide and divinyl benzene purchased from

Aldrich were used without purification. Hexane, cyclohexane,
acetone, ammonium persulfate (APS), liquid paraffin, 2,2-
azobisisobutyronitrile (AIBN), N,N -methylenebiacrylamide
(NMBAM), methacryloxypropyltrimethoxysilane (MPS) are all
analytical reactant grade and were purchased from Beijing
Chemical Reagent Company (China) and used as received. Silica
nanoparticles with an average diameter of 20 nm were provided
by Beijing Spaceflight Saide Corporation (China). Deionized water
was used throughout the study.

2.2. Preparation of PNIPAM

2.26 g of NIPAM and 0.16 g of AIBN were dissolved in 20 mL of

ethanol, this gave the NIPAM concentration of 1.0 mol/L and the
AIBN concentration of 0.05 mol/L. The solution was transferred into
a three-necked flask, filled in N2 for 30 min and reacted at 60 ◦ C
for 12 h. After reaction, the mixture was distilled to remove the
ethanol. The product was dissolved in acetone and then dropped
into hexane under stirring vigorously to remove excess monomer
and initiator. Last, the white powder was dried under vacuum at
40 ◦ C for 12 h.

2.3. Surface modification of silica nanoparticles

Scheme 1. Schematic illustration of the fabrication of TRHCs.

Silica nanoparticles (5 g, SNs) were added to 250 mL of cyclohex-
cane/water mixture (v/v, 167/1) under agitation. MPS (1.6 g) was
dropped into the silica dispersion and reacted at 70 ◦ C for 8 h. After
reaction, excess modifier was washed out by ultrasonic dispersion
and centrifugation in pure cyclohexcane. The resulting modified sil-
ica nanoparticles (MSNs) were subsequently dried under vacuum
at 70 ◦ C for 3 h.
2.4. Preparation of the hybrid capsules
The synthesis strategy is presented in Scheme 1. The formu-
lations for the preparation of hybrid capsules are summarized in
Table 1. A typical preparation procedure is described as follows
(run 2): 0.2 g of NIPAM, 0.4 g of PNIPAM, 0.006 g of NMBAM and
0.03 g of APS were dissolved in 5 g of deionized water to get the
aqueous phase. MSNs (0.3 g) were dispersed in 10 g of liquid paraf-
fin in which DVB had been dissolved to get the oil phase. A stable
pickering emulsion was generated after mixing the aqueous phase
and oil phase via digital sonicator for 14 min at 29% amplitude
and with a 40 s pause for every minute of sonication. The result-
ing pickering emulsion was poured into a 100 mL three-necked
flask equipped with a nitrogen inlet and a reflux condenser. The
emulsion was polymerized at 72 ◦ C for 12 h. The precipitate after fil-
tration was washed with water and ethanol three times. The TRHCs
were obtained after drying at 60 ◦ C under vacuum for 12 h.
2.5. Studies of controlled release from TRHCs
Rhodamine B was entrapped in TRHCs by stirring the capsules in
Rhodamine B-ethanol solution at 40 ◦ C for 2 d. These capsules were
then washed with ethanol and separated by centrifugation. The
amount of entrapped Rhodamine B was calculated from the differ-
ence between the concentration of the initial and final Rhodamine
B solutions. The release profiles of Rhodamine B–TRHCs were deter-
mined as follows: a certain amount of Rhodamine B–TRHCs were
mixed with 400 mL of phosphate buffer solution at a pH value of
7.4 in desired temperature. After each predetermined time inter-
val, 9 mL of supernatant was acquired from the release medium.
Meanwhile, fresh phosphate buffer solution was added to keep the
total volume of the suspension constant. The concentration of Rho-
damine B released was measured using a UV spectrophotometer
(UV-2501, Japan) at 549.0 nm. The cumulative release is expressed
as the released total percentage of Rhodamine B.
2.6. Characterization
(1) Optical microscopy (OM): A drop of the emulsion was placed
on a microscope slide and viewed using an optical microscope
(Olympus BX41TF) fitted with a digital camera.
(2) Transmission electron microscopy (TEM): The structures of the
capsules and MSNs were checked using the TEM (JEM-3010,
Japan). A drop of an aqueous dispersion was placed on a carbon-
coated copper TEM grid (300 mesh sizes) and allowed to air dry
for TEM characterization.
(3) Scanning electron microscopy (SEM): The morphology of the cap-
sules was checked using SEM (JSM-6701F, JEOL, Japan). Samples
were prepared by drying capsules on 0.3 cm × 0.3 cm silicon
wafers. After drying, platinum sputtering was used to apply an
ultrathin metal layer (about 0.5 nm) to enhance the quality of
images acquired in the experiments.
(4) Fourier transform infrared (FTIR) spectra measurements: The FTIR
spectra of samples were recorded in KBr pellets in a Nicolet-
8700 FTIR spectrometer in the range of 4000–300 cm−1 for 32
scans.
128 M. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 385 (2011) 126–133

Table 1
Formulations for the preparation of hybrid capsules.

Run no. PNIPAM/g NIPAM/g NMBAM/g APS/g deionized water/g MSN/g DVB/g Liquid paraffin/g

1 0.4 0.2 0.06 0.03 5 0.1 0.8 10

2 0.4 0.2 0.06 0.03 5 0.3 0.8 10
3 0.4 0.2 0.06 0.03 5 0.5 0.8 10
4 0.4 0.2 0.06 0.03 5 0.3 0.2 10
5 0.4 0.2 0.06 0.03 5 0.3 0.8 10
6 0.4 0.2 0.06 0.03 5 0.3 1.2 10
7 0.8 0.2 0.1 0.03 5 0.3 0.8 10
8 0.1 0.2 0.04 0.03 5 0.3 0.8 10
9 0.4 0.2 0.06 0.03 5 0.7 0.8 10
10 0.4 0.2 0.06 0.03 5 1.0 0.8 10

(5) Thermal analysis: Thermal gravimetric analysis (TGA) and
differential scanning calorimetry (DSC) measurement were
conducted on a thermal analysis instrument (STA-449C,
Germany) under nitrogen gas at a flow rate of 25 cm3 /min and
at a scanning rate of 10 ◦ C/min.
(6) Fluorescence microscope (FM): A drop of an ethanol dispersion
of the Rhodamine B–TRHCs was placed on a microscope slide
and viewed using a fluorescence optical microscope (Olympus
IX81) fitted with a digital camera. The excitation wavelength
was 360–390 nm.
3. Results and discussion
3.1. Formation of a pickering emulsion
A particle is held at the interface by attachment energy [15].
E = R2 (1 ± cos)
2
(1)
where R, , and  represent the radius of a particle, the oil–water
interfacial tension and the contact angle respectively. The sign in
parentheses is positive for particle removal into oil and negative for
removal into water. The wettability of particles, quantified by the
contact angle , has a great impact on the formation of emulsions.
Particles with moderate wettability will be held at the interface and
tend to stabilize emulsions. However, if the particles are either too
hydrophilic ( < 90◦ ) or too hydrophobic ( > 90◦ ), they will tend
to remain dispersion in either the aqueous or oil phase, respec-
tively. Unmodified silica particles are so hydrophilic and cannot be
absorbed on the water–oil interface to stabilize emulsions.
In this study, silanol, the hydrolysis product of MPS, was
anchored to the surfaces of SNs to confer hydrophobicity by
silanization. The TEM image of MSNs is shown in Fig. 1(a). It can
be seen that MSNs have anomalous shapes, and their average size
is about 80 nm. The FTIR spectrum of MSNs is shown in Fig. 1(b).
From the FTIR, we can see that the band at 1099 cm−1 is attributed
to a Si–O–Si stretching vibration. The band at 469 cm−1 corresponds
to a Si–O–Si bending vibration. The absorption band at 1700 cm−1

Fig. 1. (a) TEM image of MSNs, (b) FTIR spectrum of MSNs, (c) TGA curve of MSNs.
 M. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 385 (2011) 126–133 129

should be assigned to C O from silanol after modification, show-

ing that silanol has bonded to the surfaces of SNs. Fig. 1(c) shows
the TGA results of MSNs. From Fig. 1(c), we can see that there is
a weight loss of 11.2 wt% from MSNs between 300 ◦ C and 600 ◦ C,
which is assigned to the decomposition of grafted silanol, meaning
that the mass content of grafted silanol in MSN samples is 11.2 wt%.
The gross weight of the obtained MSN sample after modification is
about 5.1 g, the weight ratio of MPS involved in modification to
the gross MPS added (WMPS ) can be calculated from the following
equation:

Wsilanol ms MMPS
WMPS = (2)
Msilanol mMPS

where MMPS and Msilanol are the molecular weights of MPS and the
corresponding silanol, respectively, mMPS is the amount of MPS
added, mS is the gross weight of the obtained MSN sample, and
Wsilanol is the mass content of the grafted silanol in the MSN sam-
ple. Data for MSNs indicates that 51.8 wt% (WMPS ) added MPS is Fig. 2. Typical OM photograph (run 2) of a W/O pickering emulsion.
grafted onto the particle surface.

Fig. 3. (a) OM photograph and (b) TEM image of TRHCs, (c) magnification of the cross section of the TRHC wall, (d) SEM image of TRHCs, and (e) EDS spectrum of the TRHC
wall.
130 M. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 385 (2011) 126–133

80
1380

60
Transmittance(%)

1510
40
1630

Endo
20 469

1104 20 25 30 35 40 45 50 55 60
-20
4000 3500 3000 2500 2000 1500 1000 500 Temperature (ºC)
-1
Wavenumbers(cm ) Fig. 5. DSC curves of swollen hybrid capsules (run 2).

Fig. 4. FTIR spectrum of TRHCs.

After the monomer solution was emulsified with the MSNs
paraffin dispersion by sonication, the pickering emulsion was
obtained. Added one drop of the emulsion into aqueous and oil
phase, respectively. We found that the droplets remain spherical in
aqueous phase and dispersed immediately in liquid paraffin. This
shows that the emulsion was a W/O pickering emulsion. A typical
OM photograph (run 2) of a W/O pickering emulsion is shown in
Fig. 2. The diameters of most droplets are 10–30 ␮m.
3.2. Synthesis process of hybrid capsules
As depicted in Scheme 1, the inner aqueous solution (where
NIPAM, PNIPAM, NMBAM, and APS were dissolved) was emulsified
into liquid paraffin (where cross-linking agent DVB was dissolved)
in the presence of MSNs. A W/O emulsion stabilized by MSNs was
obtained. After the temperature was elevated, water-soluble ini-
tiator (APS) was thermally decomposed to generate primary free
radicals in water droplets. NIPAM captured the radicals and grew to
PNIPAM chains. As the polymerization proceeded at a temperature
above the phase-transition temperature of PNIPAM, the growing
PNIPAM and PNIPAM in aqueous solution became hydrophobic.
For this reason, the PNIPAM chains precipitated from the aque-
ous medium and aggregated in the oil–water interfaces [28]. At
the same time, the DVB in oil phase also diffused to the inter-
face and participated in the polymerization. As the polymerization
continued, all NIPAM, PNIPAM and the cross-linking agent DVB
reacted and an insoluble crosslinked PNIPAM network was cre-
ated at the interfaces, forming a hollow microspheric structure [29].
After washing and drying, hybrid capsules were obtained.
be seen that the capsule wall contains two layers, a solid particle
layer and a polymer layer. EDS spectroscopy (Fig. 3(e)) of the cap-
sule wall demonstrates that a large number of C, O, and Si atoms
are contained, which also proves that the capsule wall is built up
by the MSNs and polymer.
The FTIR spectrum of the TRHCs is shown in Fig. 4. Besides the
characteristic adsorption peaks of silica at 1104 and 469 cm−1 , The
bands at 1510 and 1630 cm−1 are attributed to amide stretching
and the bands at 1380 cm−1 are associated with two methyl groups
on the isopropyl group of the PNIPAM chains [30]. The spectrum
shows that the capsules are composed of PNIPAM network and
silica particles.
Fig. 5 shows the DSC result of TRHCs (run 2). It can be seen
that the volume-transition temperature of the hybrid capsules
is 27 ◦ C. The result indicates that the hybrid capsules exhibit
temperature-responsive properties. The volume-transition tem-
perature of TRHCs is slightly lower than the LCST of pure PNIPAM
(32 ◦ C) may be caused by the hydrophobicity of DVB. The incorpo-
ration of a hydrophobic polymer can decrease the LCST of PNIPAM
[31].
Fig. 6 shows the TGA result of TRHCs. Weight loss (63.1 wt%)
from TRHCs between 200 and 480 ◦ C is mainly attributed to the
decomposition of grafted silanol and the polymer layer in the cap-
sules. There is no significant weight change within the temperature
range from 480 to 700 ◦ C, indicating that the mass content of SiO2
in TRHCs is 32.5 wt%.
100
80

3.3. Characterization of TRHCs

60
Mass(%)

The OM photograph of the hybrid capsules (run 2) is shown in

Fig. 3(a). The average particle size of the capsules is about 15 ␮m,
which is in agreement with that of droplets observed from Fig. 2, 40
indicating that the hybrid capsules are duplicated from the droplets
of the pickering emulsion. Fig. 3(b) shows the TEM image of TRHCs.
20
The presence of the hollow structure is clearly revealed. The thick-
ness of the wall is about 500 nm. Fig. 3(d) shows the SEM image of
the as-synthesized capsules. 0
It is visible that sphere-like hybrid capsules are obtained. The 0 100 200 300 400 500 600 700
rugged surface morphology (inset in Fig. 3(d)) also clearly indi- Temperature( )
cates that the hybrid capsules are covered with a dense layer of
silica nanoparticles. Moreover, from the image in Fig. 3(c), it can Fig. 6. TGA curve of TRHCs (run 2).
 M. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 385 (2011) 126–133
Fig. 7. SEM images of TRHCs prepared from different particle concentrations. Particle concentrations in the continuous phase (MSNs/liquid paraffin): (a) 0.03, (b) 0.05 g/g,
(c) 0.07 g/g and (d) 0.10 g/g.
3.4. Effects of particle concentration on the preparation of hybrid
capsules
In our case, we used MSNs to stabilize droplets. Here, the
hybrid capsules prepared from five particle concentrations are
compared. The particle concentrations in the continuous phase
are 0.01 g/g (MSNs/liquid paraffin), 0.03 g/g, 0.05 g/g, 0.07 g/g and
0.10 g/g, respectively. When particle concentration was 0.01 g/g
(run 1), we did not obtain stable pickering emulsion due to the low
particle concentration. When the particle concentration increased
to 0.03 g/g (Fig. 7(a), run 2), hybrid capsules with an average diam-
eter of 10 ␮m were obtained. This is due to the high stabilization
power of MSNs and more coverage of the oil–water interface with
increasing particle concentration. In the system with a particle con-
centration of 0.05 g/g (Fig. 7(b), run 3), smaller hybrid capsules with
an average diameter of 7 ␮m were obtained. When the concentra-
tion was increased to 0.07 g/g, the average diameter of the hybrid
capsules was reduced to 5 ␮m (Fig. 7(c), run 9), when the concen-
tration was increased to 0.10 g/g, the average diameter of the hybrid
capsules was substantially invariable (Fig. 7(d), run 10), which can
be attributed to larger specific surface area with the increase of par-
ticle concentrations. The stability of water–oil interface is improved
and the coalescence of droplets is reduced. This eventually leads to
the decrease of the average particle size. As a result, the size of
the capsules depends on the number of MSNs: the higher the MSN
content, the smaller the resulting stable hybrid capsules.
3.5. Effect of PNIPAM concentration on the preparation of hybrid
capsules
PNIPAM is dissolved in water as aqueous phase, its concentra-
tion in the droplets is critical to the morphology of hybrid capsules.
131
In our case, the hybrid capsules prepared from three PNIPAM con-
centrations are compared. When the concentration was 0.02 g/mL
(run 8), the sphere like capsules were obtained (Fig. 8(a)). When the
concentration was 0.08 g/mL (run 2), the hybrid capsules deformed
slightly (Fig. 3(d)). However, when the PNIPAM concentration was
increased to 0.16 g/mL (run 7), the hybrid capsules were shown in
Fig. 8(b). From the SEM image, we can see that the capsules are
folded, which may be due to the fact that more soft PNIPAM chains
are incorporated into the polymer layer to lead the mechanical
property decreasing.
3.6. Effects of DVB concentration on the preparation of hybrid
capsules
Based on the previous work, we found that the DVB in oil phase
can diffuse to the interface and participate in the polymerization.
PNIPAM and DVB can form an insoluble crosslinked PNIPAM net-
work at the interface. As shown in Fig. 9, the hybrid capsules with
different wall thicknesses of 106, 248, 600 nm were synthesized in
the same way by increasing the amounts of DVB in the continuous
phase (runs 4, 5 and 6). The thickness of the synthesized polymer
layer increased with increasing DVB concentrations in the contin-
uous phase, indicating that more DVB can diffuse to the oil–water
interface. Therefore, the thickness of the capsule wall can be con-
trolled by adjusting the DVB concentration in the continuous phase
before polymerization.
3.7. Drug release
The hybrid capsules were swollen by Rhodamine B-rich ethanol
in order to load Rhodamine B into them. Fluorescence microscope
was used to characterize the loading of Rhodamine B into TRHCs
132 M. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 385 (2011) 126–133

Fig. 8. SEM image of TRHCs, PNIPAM concentration (g/mL, PNIPAM/water) in the aqueous phase: (a) 0.02 g/mL; (b) 0.16 g/mL.

(Fig. 10). It can be seen from the FM photograph that the hybrid
capsules possess good fluorescence. This is an indication that Rho-
damine B could be loaded into TRHCs by swelling the capsules in
Rhodamine B-rich ethanol. The loading capabilities of Rhodamine
B into TRHCs (run 2) are 2.93 mg/g (Rhodamine B/hybrid cap-
sules).
The release behavior of Rhodamine B from TRHCs at different
temperature is shown in Fig. 11. It can be seen that the capsules
exhibit a function of slow release. However, the release rate of Rho-
damine B was much faster at 45 ◦ C than at 25 ◦ C. This phenomenon
can be ascribed that when the temperature of the release medium is
below the volume transition temperature of the capsules, the driv-
ing force for the release of encapsulated Rhodamine B is merely
limited in the different concentrations of Rhodamine B inside and
outside the capsules; after the temperature is raised above the
volume-transition temperature, the hybrid capsules shrink because
of the loss of hydrogen bonds, which squeeze the Rhodamine B
out of the inner core and hence accelerate the release rate. The
released amount of Rhodamine B from TRHCs within 35 h increased
distinctly from 25.7% to 70.9% as the temperature increased from
25 to 45 ◦ C. Thus, as we expected, the thermo-sensitivity of the
capsules was improved, compared to the previous work by the
addition of PNIPAM in aqueous phase and the change of oil phase.
The reason may be that the thermal-sensitive property of PNIPAM is
affected by its molecular chain length in great extent. The molecular
chain length of PNIPM polymerized in the inner of the microcap-
sules may be influenced by the limited inner space. Parts of NIPAM
were replaced by PNIPAM, resulting in the improvement of the
thermal-sensitive property of TRHCs. The in-depth mechanism is
under investigation.

Fig. 9. TEM images of TRHCs prepared from different DVB concentrations. DVB concentrations in the continuous phase (g/g, DVB/liquid paraffin): (a) 0.02, (b) 0.08, and (c)
0.12.
 M. Wang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 385 (2011) 126–133 133

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Acknowledgement
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