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Preparation of polystyrene spheres in different particle sizes and assembly of

the PS colloidal crystals

Article in Science China Technological Sciences · November 2010

DOI: 10.1007/s11431-010-4110-5

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 SCIENCE CHINA
Technological Sciences
• RESEARCH PAPER • November 2010 Vol.53 No.11: 3088–3093
doi: 10.1007/s11431-010-4110-5

Preparation of polystyrene spheres in different particle sizes and

assembly of the PS colloidal crystals
FANG JunFei, XUAN YiMin* & LI Qiang
School of Power Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

Received September 24, 2009; accepted October 29, 2009

Monodisperse polystyrene (PS) colloidal spheres were successfully prepared through emulsifier-free emulsion polymerization
by controlling the polymerization reaction time, ionic strength of the system, concentration of the ionic copolymer (sodium
p-styrenesulfonate) and other factors. The PS colloidal spheres were assembled into colloidal crystals whose structures were
mainly face-centered cubic (fcc) close-packed. Then FDTD method was used to calculate the color-rendering characteristics of
the colloidal crystals surface. The calculated results were consistent with the experimental results.

polystyrene spheres, colloidal crystals, self-assembly, three-dimensional ordered, FDTD method

Citation: Fang J F, Xuan Y M, Li Q. Preparation of polystyrene spheres in different particle sizes and assembly of the PS colloidal crystals. Sci China Tech
Sci, 2010, 53: 3088−3093, doi: 10.1007/s11431-010-4110-5

1 Introduction At present, the familiar colloidal crystals are mainly SiO2

colloidal crystals and polymer colloidal crystals. The latter
include polystyrene (PS) colloidal crystals and polymethyl
Colloidal crystals are of the structures with a periodic ar-
methacrylate (PMMA) colloidal crystals. The emulsifier-
rangement which forms spontaneously when monodisperse
free emulsion polymerization method is a new polymeriza-
colloidal spheres are in aqueous solution. The periodic
tion method developed from the classical emulsion polym-
arrangement is similar to that of atoms in a crystal [1–3].
erization and the colloidal spheres prepared by this method
Due to the size of the colloidal spheres is generally 0.1–1.0
have the features of better monodispersity and cleaner sur-
μm, which is on sub-micron scale [1, 2], the colloidal
face [12, 13]. Therefore, this method has been widely used
crystals demonstrate an important application prospect for
for preparing monodisperse polymer colloidal spheres.
the preparation of photonic crystals in wave range of visi-
Gravitational sedimentation method, centrifugal sedimenta-
ble light and near-infrared light [3, 4]. Because the prepa-
tion method and vertical deposition method are well-known
rative process of colloidal crystals is relatively simple,
three methods for assembling monodisperse colloidal
using colloidal crystals as templates for fabricating or-
spheres into three-dimensional ordered colloidal crystals
dered macroporous materials has become a very efficient
[14]. Yu et al. [15] have successfully prepared the ordered
method in recent years [5–8]. In addition, the colloidal
SiO2 colloidal crystals by the electrophoresis-assisted depo-
crystals are widely used in sensors, filters, optical switches,
sition method.
and other optical devices due to their diffraction charac-
In this paper, monodisperse polystyrene (PS) colloidal
teristics [4, 9–11].
spheres were prepared by emulsifier-free emulsion polym-
erization method. The polymerization reaction time, ionic
strength of the system, concentration of the ionic copolymer,
*Corresponding author (email: [email protected])

© Science China Press and Springer-Verlag Berlin Heidelberg 2010 tech.scichina.com www.springerlink.com
 FANG JunFei, et al. Sci China Tech Sci November (2010) Vol.53 No.11 3089

initiator concentration and other experimental conditions 2.3 Assembly of polystyrene (PS) colloidal crystals
were altered to investigate their impacts on particle size of
the polystyrene colloidal spheres. By using the centrifugal The assembly of the colloidal crystals from polystyrene
sedimentation method, the monodisperse polystyrene (PS) spheres liquor was conducted in a centrifuge. After about
colloidal spheres of different particle sizes were assembled 24 h of centrifugation under 1000 r/min, the upper clear
into three-dimensional ordered colloidal crystals. liquid was removed and the remanent liquor was naturally
dried at room temperature. Then it was dried at 80°C in a
vacuum oven for 1 h. Finally, the three-dimensional ordered
2 Experiment colloidal crystals were prepared.

2.1 Experimental materials

2.4 Testing and characterization
Styrene (C8H8, chemically pure) was alternately washed
The particle size of the polystyrene colloidal spheres was
six times with 0.1 mol/L NaOH and deionized water in or-
measured by JEM-2100 transmission electron microscope
der to remove the polymerization inhibitor. Potassium per-
(TEM) (JEOL Corporation, Japan). The size distribution of
sulfate (K2S2O8), sodium p-styrenesulfonate (C8H7SO3Na),
the sample particles was determined with a Mastersizer Mi-
potassium hydrogen carbonate (KHCO3) and sodium hy-
cro-p laser particle size analyzer (Malvern Instruments
droxide (NaOH) were all analytically pure.
company, Britain). Infrared absorption spectra of the poly-
styrene were recorded by using a Verctor-22 Fourier trans-
2.2 Synthesis of polystyrene (PS) colloidal spheres form infrared spectrometer (Bruker Company, Germany).
The surface morphology of the colloidal crystals was char-
The polystyrene colloidal spheres were synthesized by
acterized with an S-4800 field emission scanning electron
emulsion polymerization method [8, 11, 12, 16, 17]. At first,
microscope (SEM) (Japanese Hitachi High-Technologies
a certain amount of potassium hydrogen carbonate (KHCO3)
Corporation) under an accelerating voltage of 15 kV, and
and sodium p-styrenesulfonate (C8H7SO3Na) were added
gold spray processing was done to the sample surface be-
into 200 mL deionized water and the solution was stirred
fore observation. Powder X-ray diffraction (XRD) patterns
until they were completely dissolved. Then the solution was
of the polystyrene were collected by using a D8 super speed
transferred into a 500 mL four-mouth flask, and 26 mL sty-
diffractometer (Bruker-Axs company, Germany).
rene monomer was also added into the flask. It was stirred
and reflowed under the protection of nitrogen. When the
solution was heated to 72°C, 50 mL potassium persulfate 3 Results and discussion
(K2S2O8) solution (pre-heated to 72°C) which contained a
certain amount of initiator was dropped into the solution in 3.1 The effect of reaction conditions on particle size of
30 min or so. After that the system was obturated and the polystyrene spheres
solution was stirred for 28 h.
Polystyrene colloidal spheres of different particle sizes 3.1.1 The effect of polymerization reaction time on parti-
were prepared by varying the experimental conditions. In cle size of spheres
order to analyze the effect of polymerization time on the Figure 1 exhibits a set of TEM images of polystyrene col-
particle size of the spheres, different samples were took out loidal spheres taken for different reaction times. Clearly, the
from the solution after it reacted for 2, 7, 11, 20 and 28 h, particle size grows as the polymerization time increases. In
respectively. To investigate the effects of ionic strength and the process of the styrene polymerization, a lot of polymer
ionic copolymer concentration on particle size of the nuclei are rapidly produced at first and the system becomes
spheres, the following two experiments were designed (as unstable, so they gradually come together to form latex par-
shown in Tables 1 and 2), while the other experimental ticles of larger size. As the reaction time increases, the
conditions were kept the same as before. monomer concentration in the system becomes smaller and
smaller and the growth of the polymer sphere particle size
becomes slow and finally stops [12, 17, 18].
Table 1 Effects of different amounts of potassium hydrogen carbonate
(KHCO3) 3.1.2 The effect of ionic strength on particle size of spheres
KHCO3 (g) 0.150 0.450 0.750 1.020 1.260 The relationship between the particle sizes of polystyrene
colloidal spheres and ionic strength of the system is illus-
trated in Figure 2. It is clear that the particle size increases
Table 2 Effects of different amounts of sodium p-styrenesulfonate with the increase of ionic strength. The reason may be that
(C8H7SO3Na) the stability of the emulsion in the reaction system is influ-
C8H7SO3Na (g) 0.0206 0.0310 0.0412 0.0652 0.0820 enced by the ionic strength. When the static electricity force
of the latex particles is greater than the coagulation force
3090 FANG JunFei, et al. Sci China Tech Sci November (2010) Vol.53 No.11

Figure 1 TEM images of polystyrene spheres at different reaction times. (a) 2 h; (b) 7 h; (c) 11 h; (d) 20 h; (e) 28 h.

Figure 2 Relation of sphere particle size and ionic strength.

Figure 3 Relationship of sphere particle size and ionic copolymer con-
centration.
between the particles, the system will become stable. How-
ever, the ionic strength of the system increases with the in-
creasing of KHCO3 concentration and the electrostatic re- sulfonic group, which plays a role in keeping stability of the
pulsion between the particles decreases. Therefore, the sys- latex particles. Because of such structures, when the con-
tem becomes increasingly unstable, which makes the initial centration of sodium p-styrenesulfonate increases, the con-
particles specially easy to gather, then the latex particles centrations of oligomer free radicals and sulfonic acid
grow larger and form polymer spheres of larger particle size groups both increase, resulting in the formation of more
[12, 13, 17]. active centers. Thus, the latex particles of smaller sizes in-
crease, but the speed of reaction accelerates [12].
3.1.3 The effect of ionic copolymer concentration on par-
ticle size of spheres
3.2 Particle size distribution of polystyrene spheres
Figure 3 shows the relationship between the particle size of
the polystyrene colloidal spheres and the concentration of Figure 4 shows the particle size distribution diagram meas-
sodium p-styrenesulfonate. The results shown in Figure 3 ured by laser particle size analyzer. The average size of the
illustrate that the higher the concentration of ionic copoly- polystyrene colloidal spheres is about 240 nm. The meas-
mer, the smaller the particle size of polystyrene colloidal ured result suggests that the size distribution of the colloi-
spheres. The sodium p-styrenesulfonate has a vinyl group, dal polystyrene spheres is very narrow, indicating that the
which makes it easily be triggered by initiator to generate monodispersity of the polystyrene colloidal spheres is
oligomer free radicals. In addition, it has a hydrophilic good and that it is quite easy for the colloidal spheres to be
 FANG JunFei, et al. Sci China Tech Sci November (2010) Vol.53 No.11 3091

Figure 5 IR spectra of the polystyrene.

Figure 4 Size distribution of the polystyrene spheres. absorption peaks at the wave numbers of 2921.9 and 2848.6,
corresponding to the existence of methylenes.
assembled into three-dimensional ordered colloidal arrays These IR results have confirmed that the styrene reacts
[10, 15]. to produce polystyrene through polymerization reaction. In
addition, the absorption peaks at the wave number of
3446.5 is for the stretching vibration absorption of O-H,
3.3 Infrared analysis of the polystyrene (PS)
which indicates the existence of hydroxyl. The hydroxyl
Figure 5 illustrates the infrared absorption spectra of the may come from water or hydrolysis of strong acid weak
polystyrene spheres whose average particle size is about alkali salt such as sodium p-styrenesulfonate, potassium
560 nm. Obviously, there are several absorption peaks hydrogen carbonate.
within the involved wavenumber range. There are absorp-
tion peaks at the wave numbers of 3060.8 and 3026.0 due to 3.4 Assembly and morphology analysis of the polysty-
aromatic C-H stretching vibration absorption and there are rene colloidal crystals
three absorption peaks at the wave numbers of 1600.8,
1492.7, and 1452.2 due to aromatic C=C stretching vibra- Colloidal crystals were assembled by polystyrene colloidal
tion absorption. These absorption peaks indicate the exis- spheres in several typical sizes in the experiment. The SEM
tence of benzene rings. The absorption peaks at the wave images of the polystyrene (PS) colloidal crystals (particle
numbers of 756.0 and 698.2 correspond to C-H out-of-plane sizes are about 200, 280, 450, 560 and 800 nm) are shown
bending vibration absorption and indicate that there is only in Figure 6. Colloidal crystals, also known as colloidal ar-
one substituent in the benzene ring. Figure 5 also shows the rays, are mainly arranged in the tetragonal or hexagonal

Figure 6 SEM images of the polystyrene colloidal crystals in different particle sizes. (a) 200 nm; (b) 280 nm; (c) 450 nm; (d) 560 nm; (e) 800 nm.
3092 FANG JunFei, et al. Sci China Tech Sci November (2010) Vol.53 No.11

structure. The porosity of colloidal crystals with the

tetragonal structure is much greater, which may result in
thermodynamic instability, so that the tetragonal structure
can be easily transformed into the hexagonal arrangement
that is a more stable structure. Therefore, the hexagonal
arrangement always dominates in the assembly of colloidal
crystals at room temperature [19]. As shown in Figure 6,
each sphere is tightly surrounded by six spheres to form a
hexagonal structure, although there may be some defects in
the structure in one plane. The structure defects may be
caused by the difference between particle sizes of the col-
loidal spheres, which can be minimized by strictly control-
ling the synthesis conditions to obtain spheres with uniform
particle size. Colloidal crystals are usually face-centered
cubic (fcc) close-packed and hexagonal close-packed (hcp). Figure 7 XRD patterns of polystyrene spheres in different particle sizes.
Theoretical analysis indicates that the face-centered cubic (a) 280 nm; (b) 450 nm; (c) 560 nm; (d) 800 nm.
close-packed structure is more stable in thermodynamics. It
is possible for one to make such structure dominant in col-
loidal crystals by carefully controlling experimental condi-
tions [20] in order to obtain colloidal crystals with a high
degree of regularity. Figure 6 (b) demonstrates an example
that the prepared colloidal crystals are basically of
face-centered cubic close-packed structure, in which the
hexagonal structured surface is its (111) crystal plane.

3.5 XRD analysis of the polystyrene spheres

Figure 7 shows the XRD patterns of the polystyrene spheres

with different particle sizes. Although the particle sizes of
the polystyrene spheres are different, the observed phe- Figure 8 Calculation model.
nomena reveal that a strong diffraction peak always
emerges at the position that 2θ is equal to 20°, suggesting indicates that the reflection of red light is relatively strong,
that the polystyrene spheres have certain crystallinity. which coincides very well with the observed phenomenon
that the surface of the colloidal crystals appears to be red (as
3.6 Reflection and transmission spectra analysis of the shown in Figure 10(a)). Figure 9(b) shows that the strong
polystyrene colloidal crystals reflection peak appears within the 400–500 nm bandwidth,
which belongs to the purple, indigo and green regions. Thus,
Obvious color change on the surface of the colloidal crys- it displays a complex color, which accords with the ob-
tals can be observed when the observation angle varies, but served color on the surface of the colloidal crystals. Of
there are some color differences as the particle sizes of the course, the surface of colloidal crystals also reflects light
colloidal crystals become different. Such color display on within other bandwidth, so that one can observe that the
the surface can be explained from the mechanism of physi- sample shows different colors when the observational angle
cal optics. A calculation model was established on the basis changes (Figure 10(b)).
of the microstructure of polystyrene colloidal crystals (as
shown in Figure 8). The color characteristics of the colloidal
crystals surface can be calculated by means of the finite 4 Conclusions
difference time domain method (FDTD) [21].
The calculated reflection and transmission spectra are il- Monodisperse polystyrene colloidal spheres have been suc-
lustrated in Figure 9. Distinctly, the transmission peaks of cessfully prepared through emulsion polymerization by
the surface are very strong and the reason is that there are varying the polymerization reaction time, ionic strength of
only three micro-ball layers being involved in the calcula- the system, concentration of the ionic copolymer and other
tion model. Figure 9(a) shows that the strongest reflection factors. The experimental results have indicated that the
peak appears in the 300–360 nm bandwidth, belonging to spheres particle size increases with increasing either po-
the UV region without any visible color. A strong reflection lymerization time or ionic strength of the system, but in-
peak appearing within the red bandwidth of 700–800 nm crease in concentration of the ionic copolymer leads to
 FANG JunFei, et al. Sci China Tech Sci November (2010) Vol.53 No.11 3093

Figure 9 Reflection and transmission spectra according to calculation results. (a) Sphere particle size is 280 nm; (b) sphere particle size is 450 nm.

Figure 10 Colors of the sample surface.

decrease of particle size of the spheres. The sample tests by persed spherical colloids in fluidic cells fabrications using non-photo-
lithographic methods. Langmuir, 2001, 17: 6344–6350
the laser particle size analyzer have shown that the mono-
10 Li S, Zheng J T, Zhao Y C, et al. Preparation of a three-dimensional
dispersity of the polystyrene colloidal spheres is good. The ordered macroporous titanium dioxide material with polystyrene col-
structures of the colloidal crystals are primarily face-cen- loid crystal as a template. J Appl Polymer Sci, 2008, 107: 3903–3908
tered cubic (fcc) close-packed. A calculating model which 11 Xia Y N, Byron G, Yin Y D, et al. Monodispersed colloidal spheres:
Old materials with new applications. Adv Mater, 2000, 12: 693–713
is based on the surface microstructure of the colloidal crys-
12 Li X W, Yan C H, Zhou C D, et al. Emulsifier-free emulsion copoly-
tals was established. FDTD method was used to calculate merization of styrene with sodium styrenesuifonate. Funct Polymer,
the color characteristics of the colloidal crystals surface, 1989, 2: 267–274
which were well consistent with the observed phonomena. 13 Zhu S X, Du J H, Jin X G, et al. Monodispersed polymer particles
with micron-size by emulsifier-free emulsion polymerization. Acta
Polymerica Sinica, 1998, (1): 118–123
1 Hurd A J, Clark N A, Mockler R C, et al. Lattice dynamics of colloi-
14 Yang W Y, Zheng J T. Advances of colloidal crystal templating
dal crystals. Phys Rev A, 1982, 26: 2869–2881
method to prepare three-dimensional ordered carbon materials. Carton,
2 Pan M X, Wang W H, Gast A P. Crystallization of colloidal crystal
and synthesis of three-dimensional periodic lattice cluster materials. 2005, (4): 26–30
Phys, 2000, 29: 468–475 15 Yu S C, Xu J, Xie K, et al. Assembly of sub-micrometer spheres into 3D
3 Wang C Y, Qian D X. The progress in fabrication of crystalline array periodic structure. Micronanoelectron Technol, 2003, (7/8): 129–131
and three-dimensional photonic crystals. Mater Rev, 2006, 20: 11–14 16 Holland B T, Blanford C F, Do T, et al. Synthesis of highly ordered,
4 Zhang J H, Sun Z Q, Yang B. Self-assembly of photonic crystals from three-dimensional, macroporous structures of amorphous or crystalline
polymer colloids. Curr Opin Colloid Int Sci, 2009, 14: 103–114 inorganic oxides, phosphates, and hybrid composites. Chem Mater,
5 Sadakane M, Asanuma T, Kubo J, et al. Facile procedure to prepare 1999, 11: 795–805
three-dimensionally ordered macroporous (3DOM) perovskite-type 17 Peng H X, Zhu Y H, Gu H C, et al. Synthesis of well-distributed poly-
mixed metal oxides by colloidal crystal templating method. Chem styrene microsphere by soap-free emulsion. J East China Univ Sci
Mater, 2005, 17: 3546–3551 Tech, 2002, 28: 260–262
6 Yi G R, Moon J H, Yang S M. Ordered macroporous particles by col- 18 Goodall A R, Wilkinson M C, Hearn J. Mechanism of emulsion po-
loidal templating. Chem Mater, 2001, 13: 2613–2618 lymerization of styrene in soap-free systems. J Polymer Sci: Polymer
7 Hao L Y, You M, Mo X, et al. Fabrication and characterization of or- Chem Ed, 1977, 15: 2193–2218
dered macroporous semiconductors CdS by colloidal crystal template. 19 Cong H L, Cao W X. Two array manners and packing modes in col-
Mater Res Bull, 2003, 38: 723–729 loidal crystals. Chem J Chin Univ, 2003, 24: 1489–1491
8 Li S, Zheng J T, Yang W Y, et al. A new synthesis process and char- 20 Ding J, Gao J N, Tang F Q. Fabrication of colloidal crystal array by
acterization of three-dimensionally ordered macroporous ZrO2. Mater self-assembly method. Prog Chem, 2004, 16: 321–326
Lett, 2007, 61: 4784–4786 21 Liu G P, Xuan Y M, Han Y G. Structure-color characteristic of mor-
9 Lu Y, Yin Y D, Byron G, et al. Growth of large crystals of monodis- pho butterfly. Acta Laser Biology Sinica, 2006, 15: 511–514

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