Colloids and Surfaces A: Physicochem. Eng.

Aspects 482 (2015) 338–344

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

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

Pickering emulsions stabilized by the complex of polystyrene

particles and chitosan
Shumin Zhang, Yinghao Zhou, Cheng Yang ∗
The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi
214122, 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

• The addition of chitosan induces PS

particles flocculation and improves
emulsion stability.
• Fluorescence microscopy and SEM
reveal the adsorption of chitosan and
PS particles on the emulsion droplets.
• The emulsifying mechanism of the
complex is dependent on the compo-
sition of the mixture.

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

Article history: Herein, we present a systematic investigation of oil-in-water Pickering emulsions stabilized by the com-
Received 22 April 2015 plex of polystyrene (PS) particles and chitosan (CS). The presence of both PS particles and CS resulted in
Received in revised form 10 June 2015 a stable emulsion, in contrary to those prepared with PS particles or CS alone, and the adsorption of PS
Accepted 15 June 2015
particles and CS on oil droplet surface was observed using SEM and fluorescence microscopy. In addition,
Available online 19 June 2015
the mechanism of the emulsifying ability of the complex has been studied by determining the wettability
of PS particles modified by CS, as well as the flocculation of PS particles. Specifically, at the low concen-
Keywords:
tration of CS, the emulsion was stabilized by the flocculated PS particles induced by the adsorption of CS
Pickering emulsion
Chitosan
molecules, whereas at the high concentration of CS, the emulsion was stabilized mainly by free CS.
Emulsion stability © 2015 Elsevier B.V. All rights reserved.

1. Introduction [2–14]. For example, Binks and co-workers prepared oil-in-water

Pickering emulsion is a system of dispersed droplets of one
immiscible liquid in another stabilized by solid particles. It is well
known that the wettability and flocculation of solid particles play an
important role in the formation of Pickering emulsions, and more-
over, the type and stability of resultant emulsions can be controlled
by the aforementioned two features of the solid particles [1].
Recently, much attention has been paid to the use of solid par-
ticles combined with various surfactants in Pickering emulsion
∗ Corresponding author. Fax: +86 510 85917763.
E-mail address: cyang@jiangnan.edu.cn (C. Yang).
Pickering emulsion with surface-active silica particle and cationic
surfactant. The synergism between silica particles and surfactant
led to greatly enhanced stability of the resultant Pickering emul-
sions, and the emulsions were most stable under conditions where
particles were most flocculated [3,9]. Recently, Worthen reported
that the synergism between silica nanoparticles and a weakly inter-
acting zwitterionic surfactant also resulted in a greater stability to
coalescence compared to the emulsion with either nanoparticles
or surfactant alone [11]. In addition, phase inversion could also
be induced by the addition of surfactants into particles before the
fabrication of Pickering emulsion [15–21].
Although intensive researches have been reported as mentioned
above, the unsafety and skin irritation of synthetic surfactants

http://dx.doi.org/10.1016/j.colsurfa.2015.06.029
0927-7757/© 2015 Elsevier B.V. All rights reserved.
 S. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 482 (2015) 338–344 339

makes them an undesirable choice in health and cosmetic appli-

cations. Therefore, it seems extremely essential to substitute
synthetic surfactants with some inexpensive and safe molecules.
Chitosan (CS) as a kind of alkaline polysaccharide is widespread
in nature. It is biodegradable and biocompatible, which make it
an interesting candidate in food, medicine and cosmetic fields.
Recently, CS-based emulsions have gained much attention because
of its special functions, such as hygroscopicity, moisture retention,
and antimicrobial properties. CS can be combined with surfac-
tants or proteins to improve emulsion stability or bring functional
properties to the emulsion [22–26]. For example, stable O/W emul-
sion was obtained by using a complex of CS and SDS, and the
improved emulsion stability was probably attributed to the for-
mation of thinker interface and the increasing viscosity induced by
the addition of CS [23]. What’s more, it was discovered that SDS-CS
Fig. 1. The adsorption amount of CS on PS particles and the contact angle of the CS
multilayer emulsifier could inhibit the oxidative deterioration of
modified PS particle as the concentration of CS is varied.
citral and limonene [24], and the presence of CS can provide func-
tional properties for further applications in cosmetic or medicine
[22]. Otherwise, a novel CS/TiO2 composite emulsion with antibac-
terial and anti-mildew has also been reported [25]. However, up to ducted using a double beam UV spectrophotometer (TU-1901,
now, few works has been published about stabilization of Pickering Purkinje General, China) at 800 nm.
emulsions by the complex of CS and solid particles, which have a The particle size and zeta potential of the stock dispersions of PS
plenty of advantages compared to conventional emulsions. particles and CS were measured using zeta potential and particle
In this work, a liquid paraffin-in-water (O/W) Pickering emul- sizing analyzer (ZetaPALS, Brookhaven, USA) at 25 ◦ C.
sion in the presence of CS was investigated, with polystyrene (PS)
particles as model particles. The influence of the mixture com-
position on the stability of the resultant Pickering emulsion was 2.3.2. Determination of adsorption amount of CS on the surface of
studied and especially, the emulsifying mechanism of the complex PS particles
has been proposed. Noticeably, such Pickering emulsion appeared A certain amount of CS was dissolved in acetate acid aqueous
to be more stable, in comparison with the emulsions prepared from solution (40 mL, 3 vol%) under stirring and then injected into a
the individual PS particles or CS. PS latex (40 mL, 2 wt%). After stirring for 6 h, the mixture was fil-
tered through a microfiltration membrane with the pore diameter
of 0.22 ␮m and redispersed in water by sonication. This disper-
2. Experimental section
sion/filtration cycle was repeated three times to remove the excess
CS which was not adsorbed on PS particles. The adsorption amount
2.1. Materials
of CS on PS particles was determined by measuring the CS concen-
tration in the filtrate through ninhydrin test [28]. A mixture of a
Carboxyl-functionalized polystyrene particle (PS, ca. 250 nm)
certain amount of filtrate, ninhydrin, and HAc-NaAc (pH 5) buffer
was synthesized by emulsifier-free emulsion polymerization using
solution was diluted to 3 mL with water in a test tube, and then
styrene andacrylic acid as monomers [27] 4 mol/g. Chitosan (CS)
heated by boiling water for 15 min. Subsequently, the sample was
with 90% degree of deacetylation, acetic acid (AR), glycerol (AR),
cooled in cold water and diluted to 10 mL with 60 vol% ethanol. The
ethanol (AR), ninhydrin (AR) and paraffin liquid (CR) were pur-
absorbance at 570 nm was measured on a double beam UV–visible
chased from Sinopharm Chemical Reagent Co. and fluorescein
spectrophotometer (TU-1901, Purkinje General, China).
isothiocyanate (FITC, HPLC) was purchased from Sigma–Aldrich Co.,
and all of them were used as received. Deionized water was used
throughout the experiments.
2.3.3. Measurement of contact angle
After removing the free CS, the powders of CS-modified PS par-
2.2. Preparation of PS/CS dispersion and Pickering emulsion ticles were obtained by drying in vacuum and were compressed
under a pressure of 10 metric tons. The contact angle measurement
A series of stock dispersions of PS particles and CS was obtained of water on the CS-modified PS particle in air was performed at
by mixing various volume of CS aqueous solution (2 wt%) with PS 25 ◦ C by using an optical contact angle measuring device (OCA15EC,
latex (2 wt%) under ultrasonic. DataPhysics Instrument GmbH, Germany) equipped with a CDD
Using a mixture of PS particles and CS as stabilizer, Pickering camera and the WINDROP software.
emulsions were prepared by mixing equal volume of the stock
dispersion and liquid paraffin at 10,000 rpm for 2 min using a high-
shear dispersion homogenizer (FM200, Fluko, China). The same 2.4. Characterization and stability of Pickering emulsion
process was applied for the preparation of emulsions stabilized by
either PS particles or CS alone. The type of resultant emulsions was 2.4.1. Optical microscopy
determined simply by the “drop test”. The morphology of emulsion droplets was observed using a dig-
ital microscope (VHX-1000C, Keyence Int. Trading Co. Ltd., Japan).
2.3. Characterization of PS/CS dispersion The droplet size and size distribution of the emulsions was obtained
by measuring more than 200 droplets from the optical microscopy
2.3.1. Measurement of flocculation degree image, calculating according to Eq. (1), where di is the diameter of a
The flocculation degree of PS particles was studied simply by droplet and ni is the number of droplets of diameter di . The volume
measuring the transmittance of supernatant of the mixture after mean diameter d43 is useful and sensitive to the presence of large
placing the stock dispersion for 24 h. This measurement was con- droplets.
340 S. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 482 (2015) 338–344

Fig. 2. The effect of CS concentration on the flocculation extent and zeta potential Fig. 3. The effect of CS concentration on size distribution of PS particle.
of PS particles.

2.4.3. Fluorescence microscopy

The Pickering emulsion droplets were visualized by FITC-labeled
 CS under a fluorescence microscope (Nikon 80i, Nikon Co. Ltd.,
ni ·di 4
Japan) [31,32].
(1) d43 = 
i

ni ·di 3

i 2.4.4. Stability of Pickering emulsion

2.4.2. Scanning electron microscopy (SEM)
An environmental scanning electron microscope (ESEM) (S-
4800, Hitachi, Japan) was used at a high voltage of 1.0 kV to capture
the morphology of microcapsules prepared from Pickering emul-
sion [29,30].
For O/W Pickering emulsion, creaming behaves as the release of
water under the emulsion, while coalescence behaves as the release
of oil above the emulsion or the increase of droplet size. There-
fore, the creaming stability of as-prepared Pickering emulsions was
assessed by monitoring the water-emulsion interface, whereas the
coalescence extent was estimated from the movement of the oil-
emulsion boundary as well as the variation of the average droplet
size (d43) with time [1].

Fig. 4. Vessels containing emulsions stabilized by 0.08 wt% CS (a), 2 wt% PS (b), and the mixture of PS particles and CS (c), and the corresponding optical micrographs of
emulsions shown in (b) and (c).
 S. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 482 (2015) 338–344
Fig. 5. SEM (a) and fluorescence microscope image (b) of Pickering emulsion sta-
bilized by the complex of 2 wt% PS particle and 0.08 wt% CS with equal volume of
water and oil.
3. Results and discussion
3.1. Effect of CS addition on properties of PS particles
The wettability of PS particles and the interaction between CS
and PS particles in water is responsible for their emulsifying behav-
ior in Pickering emulsions. Therefore the effect of CS addition into
aqueous dispersion of PS particle was discussed at first.
Particles became more hydrophilic after the adsorption of CS
on the surface as displayed in Fig. 1. Although the experimental
Fig. 6. Vessels containing emulsions stabilized by the complex of 2 wt% PS particles and various concentrations of CS, after preparation (a) and storage for 3 months (b).
341
Fig. 7. Average droplet diameter (d43) of the O/W emulsions stabilized by 2 wt% PS
particles and various concentrations of CS, measured after the storage for 1 day, 1.5
and 3 months at ambient condition, respectively.
values of contact angle may not exactly reflect the actual state,
it is suitable to determine the variation tendency of wettability
of the CS-modified PS particles, which can be used to explain the
adsorption ability of PS particles at the oil-water interface.
Meanwhile, flocculation of PS particles was induced by the addi-
tion of CS. Fig. 2 and Fig. 3 show the effect of CS on the flocculation
degree of PS particles as well as the zeta potential and size distri-
bution of PS particles. The zeta potential spanned from negative
to positive with the increasing amount of CS, passing through an
isoelectric point around the CS concentration of 0.065 wt%. Mean-
while, the transmittance of the supernatant reached the maximum
near the isoelectric point, indicating the formation of maximum
flocculation. This was consistent with the result of the flocculation
study by Ashmore and co-workers [33,34]. At the same time, the
particle size also reached the maximum near the iso-electric point,
whereas it was close to individual PS particle at CS concentration
between 0.20 ∼ 1.0 wt%.
3.2. CS, PS particles, and the mixture of CS and PS particles used
as stabilizer, respectively
Fig. 4 shows the digital photograph and optical microscopy
images of a series of Pickering emulsions prepared by CS, PS
particles, and the mixture of CS and PS particles as stabilizer, respec-
tively. All of these emulsions were oil-in-water type. Obviously, in
342 S. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 482 (2015) 338–344

Fig. 8. Optical micrographs of emulsions stabilized by the complex of 2 wt% PS particles and 0.01 wt% (a), 0.08 wt% (b), 0.2 wt% (c), 0.6 wt% (d), 1.0 wt% (e) and 2.0 wt% (f) CS.

the case of CS as stabilizer, the resultant emulsion was very unsta- emulsion droplets even after storage for 3 months when the con-
ble, and separated into two phases completely and rapidly. When centration of CS ranged from 0.05 wt% to 0.08 wt%. However, the
the PS particles were used as stabilizer individually, a crude emul- resultant Pickering emulsions were also unstable against coales-
sion was obtained and severe flocculation of emulsion droplets cence, when the concentration of CS was further increased. This is
occurred. However, as opposed to above-mentioned phenomena, a similar to the instability of emulsions stabilized solely by CS. On the
highly stable emulsion with small droplets and narrow size dis- other hand, it can be seen that as the concentration of CS increased,
tribution was formed as the CS and PS particles were adopted the average diameter of the emulsion droplets first decreased, then
simultaneously. Meanwhile, the adsorption of PS particles and CS increased to a maximum, and finally decreased again. This phe-
on the droplets can be observed through SEM and fluorescence nomenon could be due to the different emulsifying mechanism,
microscopy shown in Fig. 5. It is readily seen that PS particles which will be discussed in detailed in the last part.
arranged on the droplets compactly, forming a close packed shell,
which could be applied to the fabrication of microcapsules. Fig. 5b
is a fluorescence microscopy of the oil-in-water Pickering emul-
sion stabilized by the mixture of 2 wt% PS particles and 0.08 wt%
FITC-labeled CS. There are obvious green droplets and no obvious
colour was found in the continuous phase, indicating that all of the
CS adsorbed at the oil–water interface.
Therefore, we inferred that there was probably a synergistic
effect of emulsification of these two materials. In order to study
the synergistic behavior in depth, emulsions stabilized by the mix-
ture of PS particles and CS were prepared, as the composition of
mixture was varied.
Fix the concentration of PS particle in the mixture. A series of
Pickering emulsions were prepared with 2 wt% PS particles and dif-
ferent amounts of CS, as displayed in Fig. 6. Obviously, the type of
all obtained emulsions was oil-in-water. In detail, when the con-
centration of CS was less than 0.10 wt%, a clear water layer was
observed. With higher concentration of CS, a part of PS particles
desorbed at the interface and ultimately deposited at the bottom
of aqueous phase. In contrast, further addition of CS made the PS
particles remain in the emulsion phase again since there was no
obvious PS particle sedimentation. In addition, it was worth noting
that the creaming stability of aforementioned Pickering emulsions
was considered to be excellent since no more water was released
after storage for 3 months.
In Fig. 7, the long-term stability of emulsion droplets against
coalescence of above-mentioned Pickering emulsions was also
investigated by determining the size of emulsion droplets as time Fig. 9. Vessels containing emulsions stabilized by the complex of 0.08 wt% CS and
went on. It is worth noting that there was no increase in the size of various amounts of PS particles (a), and the corresponding average size of emulsion
droplets (b).
 S. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 482 (2015) 338–344
Scheme1. Schematic representation of flocculation of PS particles induced by adsorption of chitosan and the corresponding emulsification mechanism.
Fig. 8 illustrates the optical microscopy images of the aforemen-
tioned emulsions. It is obvious that the emulsion droplets stabilized
by the mixture of 2 wt% PS particles and 0.01 wt% CS were floccu-
lated seriously while those of other samples were separated from
each other. The adsorption amount of PS particles on the emul-
sion droplets reduced along with the increase in concentration
of CS. Therefore, we preliminarily inferred that the desorption of
PS particles would lead to the poor stability of obtained Pickering
emulsions.
Fix the concentration of CS in the mixture. The macroscopic
images and the droplet size distribution of emulsions prepared
with 0.08 wt% CS and different amounts of PS particles are shown in
Fig. 9. As the concentration of PS particles increased, the creaming
stability of the as-prepared Pickering emulsions increased. How-
ever, an appreciable flocculation of emulsion droplets appeared at
the relative high concentration of PS particles (e.g. 6 wt%), accord-
ing to the optical micrograph (insert in Fig. 9b). In addition, it can be
seen that the average diameter of emulsion droplets decreased first
as the concentration of PS particles increased, and then remained
relatively small. Thus, the improvement of creaming stability of as-
prepared Pickering emulsions could be attributed to the increase
of systematic viscosity, which was due to the decrease of average
diameter of emulsion droplets, as the concentration of PS particles
was increased [35].
343
3.3. Explanation for the emulsifying mechanism of PS Particles
and CS in Pickering emulsion
Obviously, the emulsifying ability of PS particles was greatly
improved by adding CS to the dispersion of PS particles before emul-
sification and then, the stability of as-prepared Pickering emulsions
was dependent on the mixture composition of PS particles and CS.
Herein, three different stabilization mechanisms were proposed
based on the above-mentioned experimental results when the PS
particles were mixed with different amounts of CS, as illustrated in
Scheme 1.
At the CS concentrations between 0.05 ∼ 0.10 wt%, the floccu-
lation of PS particles (type I) were induced by one polymer chain
adsorbing on different PS particles.[36,37] Moreover, the floccu-
lation degree of PS particles became serious as the concentration
of CS was increased. In such a case, the flocculated PS particles
possessed strong adsorption capacity and therefore, stable Pick-
ering emulsion was obtained. Furthermore, the size of emulsion
droplet decreased with the increase of flocculation degree of PS
particles, and then it reached a minimum at the concentration of
CS approach to 0.08 wt%. With higher concentration of CS ranging
from 0.20 ∼ 0.80 wt%, the flocculation of PS particles collapsed and
individual PS particles modified by CS formed (type II), accompa-
nied by few free CS molecules. Under these conditions, the resultant
344 S. Zhang et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 482 (2015) 338–344
Pickering emulsions were stabilized by the modified PS particles
and free CS molecules simultaneously. Because of the poor emul-
sifying ability of these two individual emulsifiers, the droplet size
of the obtained Pickering emulsions became larger. As the concen-
tration of CS was higher than 1.0 wt%, the structure of type III was
formed in the presence of many free CS molecules. More and more
CS adsorbed on the interface to reduce the droplet size of prepared
Pickering emulsion again.
In conclusion, synergistic interaction between PS particles and
CS occurred at the lower concentration of CS. The addition of CS to
the dispersion of PS particles led to the flocculation of PS particles
and then the enhancement of emulsifying capacity. However, com-
petitive adsorption between CS modified PS particles and free CS,
was existent at the higher concentration of CS. The resultant Pick-
ering emulsions were unstable against coalescence, because the PS
particles modified by CS became more hydrophilic and resulted
in the weak ability to absorb at the oil–water interface, which
was consistent with the observation in Fig. 8. In other words, the
adsorption of CS-modified PS particles at the interface would be
inhibited and the Pickering emulsions were mainly stabilized by
CS molecules.
4. Conclusions
A detailed investigation into liquid paraffin-in-water Pickering
emulsions stabilized by a complex of PS particles and CS has been
performed. Emulsion stability was greatly enhanced by using CS
and PS particles simultaneously, compared to those produced by
PS particles or CS alone. The emulsifying mechanism of the com-
plex has been investigated in depth through the adsorption of CS
on PS particles and the flocculation of PS particles induced by CS
adsorption. At lower concentration of CS between 0.05 ∼ 0.10 wt%,
particles flocculation was induced by the addition of CS and the
concomitant improvement of the emulsifying capacity. With fur-
ther increase of CS, the CS-modified PS particles became more
hydrophilic that were stable in the mixture, resulting in the poor
emulsifying capacity. Then at even higher concentration of CS, a
new structure formed and the emulsions were mainly stabilized
by CS. Furthermore, the addition of chitosan instead of surfactants
in the Pickering emulsion will potentially endow the emulsion anti-
bacterial property, which is expected to be applied in food, cosmetic
and pharmaceutical industries.
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