Materials Letters 141 (2015) 191–193

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Synthesis, characterization and infrared emissivity study

of SiO2/Ag/TiO2 “sandwich” core-shell composites
Xiaoyun Ye n, Chan Zheng, Xueqing Xiao, Shuguang Cai
College of Materials Science and Engineering, Fujian University of Technology, 3 Xueyuan Road, Fuzhou 350118, PR China

art ic l e i nf o a b s t r a c t

Article history: SiO2/Ag/TiO2 “sandwich” core-shell composites were successfully synthesized by combing three
Received 20 August 2014 individual synthesis steps with calcination. The as-obtained composite was composed of a SiO2 core
Accepted 17 November 2014 with an average diameter of
500 nm, full-covered Ag shell with the face-centered cubic (fcc) structure
Available online 26 November 2014
on the surface of SiO2 sphere, and an outer thin layer of TiO2 with variable crystal phases from
Keywords: amorphous to anatase. The effects of the composition and crystal form on infrared radiation properties
SiO2/Ag/TiO2 were investigated. The results revealed that the infrared emissivity value of the SiO2/Ag core-shell
Core-shell composites was remarkably decreased after the deposition of Ag shell on the surface of SiO2 core.
Composite materials Moreover, the SiO2/Ag/TiO2 core-shell composites with anatase TiO2 coating owned the lower infrared
Infrared emissivity
emissivity value than that with amorphous TiO2. Such “sandwich” core-shell structures had a relatively
Multilayer structure
low infrared emissivity value, with the lowest value down to 0.557.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, there has been increased interest in low infrared
emissivity coating due to their potential applications in civil and
military technologies such as camouflaging military tactical aircraft
and protecting vehicles from infrared detection [1]. The pigments, as
the most important factor influencing the thermal infrared stealth
coating, are investigated including metallic, colored and semi-
conducting materials. Over the past decade, many kinds of infrared
emissivity pigments such as Ag [2], Al [1] and ZnO [3] have been
developed. Metal pigments show relatively good infrared radiation
properties. And colored pigments of metal oxide are high infrared
absorbing material, resulting in the increased value of the infrared
emissivity coating. But for colored pigments, it may be advantageous
to the visible compatibility by the premise of no effect on the infrared
emissivity of the materials. Recently, ordered core-shell structures
materials have attracted considerable attentions since the shell could
offer protection to the cores and introduce new properties to the
hybrid structures [4]. The binary and ternary core-shell composite
materials have been investigated such as inorganic-metal [5], metal-
metal [6], and SiO2/Au/TiO2 [7]. These designed core-shell composites
possess interesting optical and catalytic properties originated from
special structure of metal and inorganic components alternately. Until
now, the researches on the pigments are mostly focused on the metal
n
Corresponding author. Tel./fax: þ 86 591 22863279.
E-mail address: creekyer@163.com (X. Ye).
pigments, colored pigments or their organic composites [8], but little is
known about multilayer core-shell structure composed of metal and
metal oxide, which may not only improve the infrared radiation
properties of the colored pigments but also get potential compatibility
with visible light.
In this article, SiO2/Ag/TiO2 “sandwich” core-shell composites
with low infrared emissivity were prepared through seed-growth
under ultrasonic irradiation and chemical deposition processes
(Fig. S1). The microstructure, optical properties and the influence
of the coating composition and crystal type on the infrared
emissivity of the as-prepared products were systematically
investigated.
2. Experimental section
Synthesis: Titanium isopropylate (TIPP) was purchased from
Fluka (U.S.A.). Other chemicals were purchased from Shanghai
Chemical Company. Tetraethoxysilane (TEOS, 99%) was distilled
under reduced pressure prior to use. Monodisperse silica cores were
prepared by the Stöber-Fink-Bohn method [9]. The typical prepara-
tion of SiO2/Ag/TiO2 core-shell composites was processed as follows.
5 mL of AgNO3 (0.8 mM) aqueous solution was added to a 45 mL
PVP solution in DMF ([AgNO3/[PVP]¼ 0.1), following the addition of
SiO2 spheres (0.02 wt%). The mixture was exposed to high-intensity
ultrasound irradiation(20 kHz, 800 W/cm2) for 30 min at 28 1C. The
obtained mixture was centrifugally separated and ultrasonically
washed. The above procedures were repeated three times and

http://dx.doi.org/10.1016/j.matlet.2014.11.085
0167-577X/& 2014 Elsevier B.V. All rights reserved.
192 X. Ye et al. / Materials Letters 141 (2015) 191–193

Fig. 1. TEM and HRTEM images of SiO2 spheres during successive Ag and TiO2 deposition steps.

signed as SiO2/Ag(sdx, x ¼ 1–3). 10 mL of the seeded colloid particles (101)

aqueous solution (0.1 wt%) was mixed with 10 mL of AgNO3 solution TiO
(1.5 mM), followed by 25 μL of formaldehyde and 25 μL of ammonia.
The above procedures were also repeated three times to obtain SiO2/ * Ag

Ag core-shell composites. Finally, SiO2/Ag core-shell composites

(0.1 wt%) were dispersed in 100 mL ethanol, followed by the addi- (200)
(004) (211) (204)
Intensity(a.u.)

tion of TIPP (0.01 M) dropwise. The mixture was stirred and refluxed (215)
for 1.5 h. After centrifugally separating and washing, the resulting c
(101)
SiO2/Ag/TiO2 composites were calcined at 200 1C and 650 1C.
(111) (200) (211) (204)
Characterization: Transmission electron microscopy (TEM) was
performed with a JEM-2100 microscope operating at 200 kV. * b
(111)
Fourier-transform infrared spectroscopy (FT-IR) was carried out on a
Nicolet Magna-IR 750 spectrometer (USA). X-ray diffractometry (XRD) * (200) (220) (311)
was performed with an X-ray diffractometer (XD-3 A) operating at * * * a
40 kV and 30 mA with CuKα radiation. UV–vis absorption spectra
were measured with a Shimadzu UV-2201 spectrophotometer. The
20 40 60 80
photoluminescence spectra were obtained from a Perkin Elmer LS55
fluorescence spectrophotometer with 410 nm excitation wavelength. 2θ ( )
Infrared emissivity values of the samples were carried out on IRE-I Fig. 2. XRD curves of SiO2/Ag/TiO2 multilayer composites: (a) without calcination;
Infrared emissivity measurement instrument of Shanghai Institute of (b) calcined at 200 1C; (c) calcined at 650 1C.
Technology and Physics, China.

3. Results and discussion
Fig. 1 shows the TEM observation of the samples. Pure SiO2 spheres
with uniform size of
500 nm and good dispersion are gained
(Fig. 1A), on which Ag seeds of
20 nm are successfully deposited
after AgNO3 reduction. Moreover, the density of Ag on the surface of
SiO2 is significantly increased by cycled step (Figs. 1B and C). These Ag
seeds provide the growing points for the Ag shell growth. In Figs. 1D
and E, the SiO2/Ag core-shell composites with the Ag coating of some
discontinuous and further package of complete Ag shell are obtained.
Finally, a lamella of TiO2 is further deposited onto the surfaces of SiO2/
Ag core-shell composites (Fig. 1F). HRTEM taken at the edge of the Ag
and TiO2 layers further illustrates the morphology of the composites.
In Figs. 1G and H, the fringe spacing of the 2.36 and 3.6 can be indexed
to the (1 1 1) reflection of face-centered cubic (fcc) Ag and the (1 0 1)
reflection of anatase TiO2.
The XRD patterns of the multilayer samples are given in Fig. 2. The
diffraction peaks in the XRD pattern of the composites without
calcination correspond to the typical fcc Ag (Fig. 2a). A wide peak
due to amorphous SiO2 is also detected. While the diffraction peaks
almost correspond to anatase TiO2 after annealing (Fig. 2b). The type
diffraction peak at 2θ ¼25.31 appears, which can be indexed as (1 0 1)
diffraction of anatase TiO2, and other peaks of Ag shell are almost
completely covered. Along with the further increased heat treatment
temperature, the composites exhibit clear and sharp peaks corre-
sponding to anatase TiO2, owing to superior crystalline and increased
particles size after roasting (Fig. 2c).
The UV–vis and PL spectra of the SiO2 spheres before and after Ag
and TiO2 shells deposition are illustrated in Fig. 3. Obviously, there is
no significant peak for SiO2 due to its optical inertness and scattering
of light under the present experimental conditions [10] (Fig. 3a). After
loading Ag, a broad absorption peak around 415 nm appears in UV–vis
curves, which is due to surface plasmon excitation of metal Ag
 X. Ye et al. / Materials Letters 141 (2015) 191–193 193

absorption. High reflection and low absorption are both beneficial

to improve the infrared radiation property of the composites. After
introduction of TiO2 as protective layer, the SiO2/Ag/TiO2 compo-
sites still show a relatively low infrared emissivity value. Moreover,
the infrared emissivity values are obviously reduced with good
crystallinity of TiO2 layer, which is caused by the reduction of the
lattice distortion and the formation of complete lattice with the
growth of the TiO2 nanoparticles after heat treatment [13].

4. Conclusion

The SiO2/Ag/TiO2 core-shell composites, with low infrared

emissivity values during 8–14 μm wavelengths, were obtained by
combining seed-growth and chemical deposition steps. Completed
Ag shell with the fcc structure was coated onto the surface of SiO2.
An outermost thin layer of TiO2 varied in the crystal types from
amorphous to anatase after heat treatment. The infrared emissiv-
Fig. 3. UV–vis absorption spectra of (a) bare SiO2 spheres; (b) SiO2/Ag core-shell ity value of the SiO2/Ag core-shell composites was remarkably
composites; (c) TiO2-decorated SiO2/Ag core-shell composites; The inset is the
corresponding PL spectra.
decreased than that of pure SiO2 after the Ag shell deposition. The
sandwich structure with anatase TiO2 coating owned the lower
infrared emissivity value than with amorphous TiO2 and downed
Table 1
to 0.557. The introduction of the Ag greatly improves the infrared
Infrared emissivity values of samples.
radiation properties of the colored pigments. Therefore, the SiO2/
Samples Infrared emissivity (εTIR at 8–14 μm) Ag/TiO2 “sandwich” core-shell pigments can be used as a novel
low infrared emissivity pigment to improve the stealthy perfor-
SiO2 0.785 mance of the infrared radiation coating and even potential
SiO2/Ag(sd3) 0.517
SiO2/Ag 0.410
compatibility with visible light.
SiO2/Ag/TiO2(amorphous) 0.685
SiO2/Ag/TiO2(anatase phase) 0.557
Acknowledgments

This work was financially supported by the National Natural

(Fig. 3b). Further deposition of TiO2 layer later, the position absorption
Science Foundation of China (Grant No. 61108056), the Natural
peak of the Ag shell slightly red shifts of
8 nm (Fig. 3c). It can be
Science Foundation of Fujian Province (Grant No. 2012J01186), the
explained that the Ag shell inside is relatively isolated by covering of
Scientific Development Pre-study Foundation of Fujian University
the TiO2 layer, resulting in the reduced electrostatic interaction
of Technology (Grant No. GY-Z11064).
between Ag shells [11]. In the PL spectra, it is observed three peaks
of two weak blue-green and one strong orange emission in the visible
region at
480 nm,
520 nm and
610 nm respectively, which are Appendix A. Supporting information
attributed to the interaction of Ag shell and SiO2 substrate as well as
the size and quantity of Ag particles [10], Ag2þ 3 species formed by Supplementary data associated with this article can be found in the
association of a silver Ag0 atom and two Ag þ ions [12] and the online version at http://dx.doi.org/10.1016/j.matlet.2014.11.085.
structural defects and other impurity of the composites. The spectra
also show that after further modification of the Ag shell by anatase
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