COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 67 (2007) 34873490
www.elsevier.com/locate/compscitech

Short communication

Fabrication of thermochromic composite using

monodispersed VO2 coated SiO2 nanoparticles
prepared by modied chemical solution deposition
Hisao Suzuki a, Kenji Yamaguchi a, Hidetoshi Miyazaki b,*

a
Department of Materials Science, Faculty of Engineering, Shizuoka University, 3-5-1, Johoku, Hamamatsu, Shizuoka 432-8561, Japan
b
Department of Material Science, Faculty of Interdisciplinary Science and Engineering, Shimane University, 1060, Nishikawatsu-cho,
Matsue, Shimane, 690-8504, Japan

Received 16 May 2007; received in revised form 27 June 2007; accepted 11 July 2007
Available online 20 July 2007

Abstract

Monodispersed thermochromic VO2 particles were fabricated by VO2 coating onto monodispersed SiO2 nanoparticles with the mod-
ied chemical solution deposition technique using vanadium isopropoxide solution and monodispersed SiO2 particle suspension solution.
The average size of the resultant VO2SiO2 particle was 57 nm and the coating thickness of the VO2 layer was 6 nm. A thermochromic
composite was fabricated using the VO2SiO2 particles and a poly lactose acid polymer as a transparent matrix, and the transmittance of
the composite at a high temperature was 10% less than that at a low temperature.
2007 Elsevier Ltd. All rights reserved.

Keywords: A. Oxides; A. Smart materials; D. Transmission electron microscopy (TEM); E. Solgel methods

1. Introduction In a previous study, we reported the fabrication of size con-

Vanadium dioxide VO2 exhibits a semiconductor-to-
metal transition at about 68 C accompanied by a crystal-
lographic structure change [1,2]. This phase transition
causes abrupt changes in the optical and electrical proper-
ties. VO2 therefore has potential applications as a thermal
or optical switch, or as a thermochromic smart window [3
8]. There are several works focused on applications; a com-
posite involving VO2 powders in polymeric matrices [9],
and coating nano-size VO2 powders on glass substrate [10].
In previous, oxide thin lms or oxide thin lm precur-
sors have been fabricated by the chemical solution deposi-
tion (CSD) [8,11,12] since the CSD method is one of the
useful coating method. Thereupon, the authors have
designed a coating onto the particle surface homoge-
neously, with modifying above mentioned CSD method.
trolled VO2 nanocoated SiO2 (hereinafter VO2SiO2) parti-
cles with monodispersion by coating a vanadium oxide
layer onto the monodispersed SiO2 particle [13], with mod-
ied chemical solution deposition. The VO2 coating on
SiO2 particle was carried out by modied chemical solution
deposition. However, this method needs annealing at high
temperature in an inert atmosphere and the products
include a second phase, i.e. V4O9 or another phase.
This study aimed to fabricate size controlled single
phase VO2 nanoparticles with monodispersion. Fig. 1
shows a schematic of this study. The authors also prepared
a thermochromic composite using VO2SiO2 nanoparticles
and poly lactose acid (PLA), and evaluated the thermo-
chromic properties.
2. Experimental

*
Corresponding author. Tel./fax: +81 852 32 8893. A suspension of monodispersed ultrane SiO2 particles
E-mail address: miya@riko.shimane-u.ac.jp (H. Miyazaki). was prepared by a previously reported method [14]. The

0266-3538/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2007.07.004
3488 H. Suzuki et al. / Composites Science and Technology 67 (2007) 34873490

SiO2 particle scattering using an Otsuka Denshi ELS-800/LEZA600.

Transmittance of the VOxSiO2 particle/PLA composite
was measured using a JASCO FT-IR 460Plus in the wave-
VO2 coating
length range of 2.58.5 lm.

3. Results and discussion

VO2
Size controlled Size controlled
SiO2 particle VO2 / SiO2 particle Figs. 2 shows (a), (b) selected TEM images and (c) an
electron diraction (ED) pattern for the resultant VOx
Fig. 1. Schematic of the fabrication of monodispersed VO2 coated SiO2 SiO2 particles. From Fig. 2a, the resultant VOxSiO2 parti-
ne particles. cles formed a sphere-like shape with an average particle
size of 55 nm. As shown in Fig. 2b, the crystalline particle
resultant SiO2 particle size d could be controlled by the with the size of 5 nm was coated homogeneously on
concentration of TEOS [TEOS] and ammonia [NH3], and the surface of the core SiO2 particle, thus a coating layer
the relation was as follows:
d NH3 =TEOS
In this study, to fabricate monodispersed SiO2 particles
with a particle size of 50 nm, the [NH3]/[TEOS] ratio was
controlled to 0.45. The SiO2 suspension included water;
therefore, in the suspension solution water was replaced
with 1-buthanol by distillation at 110 C to remove water.
Vanadium isopropoxide precursor solution was pre-
pared at a concentration of 0.5 mol/l in 2-propanol and
2-methoxyethanol mixed solvent (mixing ratio of 1:1),
and then reuxed at 90 C for 2 h. In our previous study,
it was demonstrated that VO2 coating on SiO2 particle
could be eectively fabricated using acetic acid, which
worked as a chelating acid in the solution [13]. Thus, in this
study acetic acid was added to the precursor solution as a
chelating regent to eectively coat the VOx precursor onto
the SiO2 particle. These were mixed to a [V]/[CH3COOH]
mixing molar ratio of 3/10.
The SiO2 particle suspension and vanadium isopropox-
ide solution were mixed with [V]/[Si] at a molar ratio of
1:1. Hydrolysis was then carried out for the solution with
a [water]/[V] molar ratio of 2:1. Precursor VOxSiO2 parti-
cles were suction-ltrated, dried at 200 C in air, and then
annealed at 600 C for 1 h in a nitrogen atmosphere.
To evaluate the thermochromic properties of the resul-
tant VOx coated SiO2 particles (hereinafter, VOxSiO2 or
VO2SiO2 particles), the authors fabricated a VOxSiO2
particle/transparent resin (poly lactose acid, PLA)
composite. Here, PLA does not show any thermochromic
property. PLA was mixed into N,N-dimethylholmamid at
a concentration of 100 g/l, and dissolved at 100 C. VOx
SiO2 particles were put into the PLA solution with a vol-
ume fraction of 2%. The mixture was placed between at
glass sheets and dried at room temperature before the
product was removed from between the glass sheets.
Microstructure and crystallographic structure of the
resultant VOxSiO2 particles were observed by TEM and
electron diraction using a Hitachi HR9000NAR. The
structure of the VOxSiO2 particles was characterized by
XRD using Rigaku RINT-2100 with Cu Ka at room tem-
perature. Particle size distribution of the resultant VOx Fig. 2. Selected TEM micrographs of (a), (b) the VOx coated SiO2 particle
SiO2 particles was evaluated by electrophoretic light and (c) an electron diraction pattern for the VOx coated SiO2 particle.
 H. Suzuki et al. / Composites Science and Technology 67 (2007) 34873490 3489

thickness was estimated about 5 nm. The crystalline phase 100 50

Frequency accumulation (%)

SiO2
was observed by ED (Fig. 2c), and the structure of the
phase was seen as VO2. 80 VO2-SiO2 40

Frequency (%)
To evaluate the structure of the resultant VOxSiO2 par-
60 30
ticle, XRD measurements were also carried out for the par-
ticles. Fig. 3 depicts the XRD patterns for the VOxSiO2
40 20
particle. All the diraction peaks can be assigned to a
VO2 of the JCPDS 43-1051. The electron diraction pat- 20 10
tern and the XRD results revealed that VO2SiO2 monodi-
spersed particles could be obtained successfully. 0 0
Guinneton et al. reported the fabrication of VO2 nano- 20 40 60 80
powder by reduction of VO2(B) [10]. Zheng et al. fabricated Particle size (nm)
VO2 nanopowder by pyrolysis of the precursor [NH4]5- Fig. 4. Particle size distribution of precursor SiO2 particles (the dashed
[(VO)6(CO3)4(OH)9] 10H2O [15]. These reported speci- line and the open circles) and the VO2 coated SiO2 particles (the solid line
mens were observed considerable aggregation. These VO2 and the solid circles).
nanopowders were fabricated by reduction or pyrolysis of
a larger precursor powder; hence the precursor materials particle/PLA composite was prepared using the above
were much larger than the resultant specimen. Therefore, noted specimen and PLA; the appearance can be seen in
it assumed that the resultant VO2 nanopowder was consid- a photograph in Fig. 5a. The composite was placed on
erably aggregated in those investigations [10,15]. However,
aggregation was not observed in the present VO2SiO2 par-
ticles. The VO2SiO2 particles were prepared using small
sized precursor VOxSiO2 particles; therefore, it assumed a
that the present VO2SiO2 nanoparticles were obtained
without aggregation.
Size distributions of the monodispersed SiO2 particles
and the resultant VO2SiO2 particles were measured by
electrophoretic light scattering. The results are shown in
Fig. 4. The size of the precursor SiO2 particles was about
45 nm, which was very close to the target of 50 nm. The
average particle size of the VO2SiO2 particles was
57 nm; therefore, a 6 nm thickness of VO2 was coated onto 100
the SiO2 particles. These results agreed well with the result b
Transmittance (%)

of TEM observation and demonstrated that monodi- 80

spersed VO2SiO2 particles could be successfully fabricated
60
by our method.
In previous, the authors successfully fabricated IR-opa- 40
que and visible-transparent composite lms using ITO ne
particles and urethane polymer [16], and UV-opaque visi- 20
ble-transparent composite lms using ZnO ne particles 0
and urethane polymer [17]. Therefore, the authors tried 2.5 4.5 6.5 8.5
to fabricate a thermochromic composite using the VO2 Wavelength ( m)
SiO2 particle for smart window application. A VO2SiO2
100
(low temp. phase) c
Transmittance (%)

80
(101)

60
(211)
Intensity (a.u.)

40
(220)
(202)
(200)

20
(211)
(222)
(101)

(210)
(212)

0
2.5 4.5 6.5 8.5
Wavelength ( m)
10 20 30 40 50 60
2 (deg) Fig. 5. (a) Photograph of a VO2SiO2 particle/PLA composite at room
temperature, and the transmittance in IR range for the VO2SiO2 particle/
Fig. 3. XRD pattern for the VOx coated SiO2 particle. PLA composite (b) at room temperature and (c) at 80 C.
3490 H. Suzuki et al. / Composites Science and Technology 67 (2007) 34873490
transparent paper on which was printed the letter VO2,
and the photograph was took at room temperature.
Fig. 5b and c depicts the transmittance in the range 2.5
8.5 lm for the VO2SiO2 particle/PLA composite at room
temperature and 80 C, respectively. The peaks at 3300,
6860, and 7200 nm were attributed to the absorption of
PLA. The transmittance of the composite at a high temper-
ature was 10% less than that at a low temperature; thus the
thermochromic composite could be successfully fabricated
using the VO2SiO2 particle and PLA composite.
4. Conclusion
In conclusion, VO2SiO2 particles were successfully fab-
ricated by a chemical solution route using a vanadium iso-
propoxide solution and a monodispersed SiO2 particle
suspension solution. VO2SiO2 particle size could be con-
trolled to 57 nm, and the thickness of coated VO2 was
6 nm. A VO2SiO2 particle/PLA composite was fabricated
and exhibited thermochromic properties. The transmit-
tance of the composite at a high temperature was 10%
lower than that at a low temperature at the IR wavelength
range.
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