724 Journal of the Chinese Chemical Society, 2008, 55, 724-731

Microwave Absorption and Infrared Stealth Characteristics of Bamboo

Charcoal/Silver Composites Prepared by Chemical Reduction Method

Tzu-Hao Tinga ( ), Kuo-Hui Wua* ( ), Jen-Sung Hsub ( ),

b
Ming-Ho Chuang ( ) and Cheng-Chien Yangb ( )
a
Department of Applied Chemistry and Materials Science, Chung Cheng Institute of Technology,
National Defense University, Tahsi, Taoyuan, Taiwan, R.O.C.
b
Chemical Systems Research Division, Chung Shan Institute of Science and Technology,
Taoyuan, Taiwan, R.O.C.

Bamboo charcoal coated with silver (BC/Ag) was prepared by activation and chemical reduction pro-
cesses at different AgNO3 contents (10-30 wt.%). The spectroscopic characterizations of the formation
processes of BC/Ag composites were studied using X-ray diffraction, scanning electron microscopy and
transmission electron microscopy. These composites were introduced in epoxy resin to be a microwave
absorber and mixed polyethylene to be an infrared stealth plate. Microwave absorbing properties were in-
vestigated by measuring complex permittivity, complex permeability and reflection loss in the 2-18 and
18-40 GHz microwave frequency range using the free space method. The thermal extinction measure-
ments in the 3-5 and 8-12 mm were done to evaluate the shielding affectivity of infrared. The results
showed that a significant thermal extinction and a wider absorption frequency range could be obtained by
adding silver to bamboo charcoal.

Keywords: Bamboo charcoal; Silver; Microwave absorption; Thermal extinction.

INTRODUCTION stealth (low infrared emissivity) material and MAM sepa-

Microwave absorbing materials (MAM) have been
widely used to prevent or minimize electromagnetic reflec-
tions from large structures such as aircraft, ships and tanks
and to cover the walls of anechoic chambers.1-5 But in gen-
eral, the MAM layer is highly emissive and causes high
temperatures. For an object with a high temperature, which
is in the order of hundreds of degrees centigrade, such as
the exterior surface of an aircraft, the peak radiation is dis-
tributed in the 3-5 and 8-12 mm bands.6 The high emittance
of the exterior surface of the aircraft caused by the MAM
greatly increases the probability of being detected by an in-
frared detector. And because military objects have higher
temperatures than the background, they have higher bright-
ness in the infrared image and the background has lower
brightness and contrast.7-11 In order to decrease the high
temperature from the hot MAM layer, it is possible to add
an additional material with low infrared emittance to the
MAM layer. Two technical concepts can be employed in re-
alizing the preceding purposes.12 The first is to develop a
structure which is effective in all the infrared and the mi-
crowave regions. This is a double-layer or multi-layer com-
patible absorbing plate. The second is to design the infrared
rately and then to combine these materials into a single-
layer compatible absorber which is effective in the desired
properties.
Very little has been published on microwave absorb-
ers with low infrared thermal exitance, such as bamboo
charcoal coated with silver particles. Such materials have
special interest because of new and often unusual micro-
wave absorbance with infrared stealth properties. In this ar-
ticle, we present a novel approach to synthesizing bamboo
charcoal/silver (BC/Ag) composites. The origin of their
properties is also discussed on the basis of the structural
characterization, including X-ray diffraction (XRD), scan-
ning electron microscopy (SEM) and transmission electron
microscopy (TEM). Microwave absorbing properties of
the BC and BC/Ag reinforced epoxy resin composites were
tested at 2-18 and 18-40 GHz microwave frequencies using
the free space method, which is known as an adequate
method for measuring anisotropic and inhomogeneous ma-
terials like composites. 13 The characteristic of infrared
stealth of the BC and BC/Ag polyethylene composite plate
was studied with infrared thermal-imaging equipment in
samples of 3-5 and 8-12 mm.
Bamboo Charcoal Coated with Silver (BC/Ag)
EXPERIMENTAL
Preparation of BC/Ag and epoxy resin-BC/Ag com-
posites
The BC powders (particle size < 10 mm, Taiwan
Paiho) were activated with surfactant sodium alginate un-
der stirring for 1 h. The as-prepared BC powders (2 g)
were immersed into 100 mL of biamminesilver nitrate
([Ag(NH3)2]NO3) solutions, which were formed by adding
aqueous ammonia into AgNO3 solution at room tempera-
ture. After stirring for 1 h, dilute aqueous solutions of
hydrazine monohydrate were separately prepared and were
introduced to the BC-[Ag(NH3)2]NO3 solutions in appro-
priate quantities (molar ratio 1:1 with respect to silver ni-
trate) by a syringe. The color of the solutions changed to ei-
ther gray or gray black due to reduction of Ag+ to Ag. Stir-
ring was continued under inert atmosphere at room temper-
ature for another 4 h. The BC/Ag particles were separated
and washed with deionized water and ethanol, then dried in
vacuum at 60 C overnight. The composite weight ratios of
BC and Ag were 1:0.1 (BC/Ag-1), 1:0.2 (BC/Ag-2) and
1:0.3 (BC/Ag-3), respectively.
The absorbing composite materials were prepared by
molding and curing the mixture of BC and BC/Ag powders
and a thermal-plastic epoxy resin. The mixing ratio of spec-
imen powders to epoxy resin was 1:2 by weight. Molding
was carried out in a hydraulic press at 5 Mpa pressure and
80 C for 1.5 h, obtaining specimens of 15 cm 15 cm with
a thickness of 0.2 cm for reflectivity measurements.
Each component of the infrared adsorption plates was
mixed together by dry polyethylene to obtain a powder
mixture. The composites of the polyethylene with BC and
BC/Ag composite powders were controlled by weight. The
powder mixtures having the above powders were carried
out in a hydraulic press at 5 Mpa at 120 C for about 4 h to
form a 15 cm 15 cm 0.1 cm for the infrared image test.
Experimental techniques
The phase identification of the samples was per-
formed with X-ray diffraction with Cu Ka radiation. The
particle morphology was observed with a JEOL JEM-
200CX scanning electron microscope as well as a Philips
CM-200 transmission electron microscope. The permit-
tivity (e, e) and permeability (m, m) of the composites
were measured by using a HP8722ES network analyzer in
the frequency range of 2-18 and 18-40 GHz. The sample
under test was positioned on an aluminum panel. For a mi-
crowave-absorbing layer terminated by a short circuit, the
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 725
normalized input impedance related to the impedance in
free space, Z, and reflection loss (R.L.) related to the nor-
mal incident plane wave are given by theory of the absorb-
ing wall,14
m* 2pt
Z= tanh j m * e* (1)
e* l
Z -1
R. L. ( dB ) = 20 log (2)
Z +1
where l is the wavelength and t is the thickness of speci-
men. e* is the complex permittivity = e je, where e and
e are the real and the imaginary parts of e*, respectively.
e, associated with electric field loss, results mostly from
electric-dipole polarization at microwave frequencies. m*
is the complex permeability = m jm, where m and m are
the real and imaginary parts of m*, respectively. m, associ-
ated with magnetic field loss, results from magnetic-dipole
magnetization. Further, the loss tangent of the dielectric/
magnetic can be expressed as tan de = e/e and tan dm =
m/m, respectively. The infrared stealth effects were mea-
sured with FLIR MERLIN (3-5 mm) and FLIR SC2000
(8-12 mm) infrared thermal-imaging equipment. An infra-
red thermal image is an image captured by a thermal cam-
era to display infrared radiation. Therefore an infrared ther-
mal image is a suitable tool to measure the object surface
temperature, and the reduced thermal exitance resulting
from either low temperature or low emittance reduces the
chance of thermal infrared detection. The test set-up is il-
lustrated in Fig. 1. For this experiment the sample under
test was a 15 cm 15 cm 0.1 cm low-density polyethyl-
ene (LDPE) plate. The amount of BC and BC/Ag hybrids in
Fig. 1. Set-up of infrared thermal image testing.
726 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 Ting et al.

the LDPE was controlled to be ~0.002 g cm3.

RESULTS AND DISCUSSION

Structure characterization
Fig. 2 shows the X-ray diffraction patterns of the BC
and BC/Ag composites, respectively. The XRD pattern
measured from the BC is showed as an amorphous mate-
rial. The broad peaks were from the (002) planes of the
amorphous graphite phase in the bamboo charcoal.15 Sev-
eral small peaks besides the main broad peaks from (002)
and (100) planes of amorphous graphite appeared in the
X-ray diffraction patterns of the bamboo charcoal. In the
spectrum of the BC, between 20 and 30 is seen as a broad Fig. 2. XRD spectra of (a) BC, (b) BC/Ag-1, (c) BC/
plateau of mixed amorphous SiO2 and C; also the graphite Ag-2 and (d) BC/Ag-3 composites.

Fig. 3. SEM photographs of (a) BC, (b) BC/Ag; TEM photographs of (c) BC, (d) BC/Ag-3 and (e) EDX spectrum of the
BC/Ag-3.
Bamboo Charcoal Coated with Silver (BC/Ag)
Fig. 4. Frequency dependences of the complex permittivity, complex permeability and loss tangent of dielectric/magnetic of
epoxy-BC and epoxy-BC/Ag composites in 2-18 GHz.
and SiC phases are apparently formed in the bamboo char-
coal.16 Its intensity gradually decreases with increasing Ag
content. The XRD of the BC/Ag composites are in good
agreement with the literature values of silver nanoparti-
cles.17 All the prominent peaks at 2q values of about 38, 44,
65 and 77 represent the 111, 200, 220 and 311 Braggs re-
flections of face-centered cubic crystalline silver. Further-
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 727
more, an increase of the amount of AgNO3 in BC induced
the obvious enhancement of characteristic peaks of silver,
implying the development of larger and highly crystalline
silver nanoparticles. Therefore, we can estimate the size of
nano-Ag grain (2q = 38) using Scherrers formula D =
0.9l/bcosq, where D is the crystallite size in nm, l is the ra-
diation wavelength (0.154056 nm for Ka1), b is the band-
728 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
width at half-height and q is the diffraction peak angle.18
The calculated crystallite sizes are 40, 55 and 75 nm for
BC/Ag-1, -2 and -3, respectively.
SEM and TEM photographs were used to evaluate the
surface morphology and size distribution of silver depos-
ited on the BC surface. As shown in Fig. 3, ultra-fine and
aggregated silver particles were homogeneously distrib-
uted on the surface of the BC. The pure BC had a porous
surface. The silver particles are granular in nature and seem
to be nanosized, typically in the range of < 100 nm. This
agreed with the XRD results. It shows that silver content in-
creases with increasing the initial concentration of AgNO3
solution. The surface composition of BC/Ag composites
was distinctly determined with EDX (Fig. 3e). Therefore, it
can be assumed that Ag nanoparticles are deposited on the
surface of the BC particles.
The microwave adsorbing properties of BC and
BC/Ag composites
Fig. 4 shows the relative permittivity e* and the rela-
tive permeability m* of epoxy-BC and epoxy-BC/Ag com-
posites measured in the frequency range of 2-18 GHz. The
real part and the imaginary part of permittivity (e, e) for
epoxy-BC and epoxy-BC/Ag composites are larger than
those composites of the real part and imaginary part of per-
meability (m, m) in the frequency range of 2-18 GHz. The
real and imaginary parts of permeability (m, m) remained
practically constant in the whole frequency range. The dis-
sipation factors are represented by the dielectric loss (tan
de) and magnetic loss (tan dm). The values of tan de for both
epoxy-BC and epoxy-BC/Ag composites are larger than
those of tan dm in the whole frequency range, which sug-
gests that microwave absorption enhancement of compos-
ites results mainly from dielectric loss rather than magnetic
loss. These characteristic electromagnetic properties can
be applied to the microwave absorbing material.
Fig. 5 shows absorption characteristics of epoxy-BC
composite and epoxy-BC/Ag composites in the frequency
range of 2-18 GHz. It can be seen that epoxy-BC/Ag com-
posites have a more obvious effect on microwave absorb-
ing properties than epoxy-BC composite does. The speci-
men of the BC powder showed only one band at 6.5 GHz
with -6.2 dB in reflection loss. Among the epoxy-BC/Ag
composites, the powder prepared from the silver content of
20 wt.% (BC/Ag-2) exhibited two relatively pronounced
absorption bands at 4.8 and 15 GHz, with the reflection
Ting et al.
losses of -13 dB and -5 dB, respectively. Clearly demon-
strated is that the intensity and frequency of the reflection
loss maximal for the composite also depends on the silver
content.
Fig. 6 shows frequency dependence of the complex
permittivity, complex permeability and dielectric/magnetic
loss tangent of epoxy-BC and epoxy-BC/Ag composites in
18-40 GHz. It can be seen that the real part and the imagi-
nary part of permittivity (e, e) for epoxy-BC and epoxy-
BC/Ag composites are larger than those of the real part and
the imaginary part of permeability (m, m) in the frequency
range of 18-40 GHz. The values of tan de for both epoxy-
BC and epoxy-BC/Ag composites are larger than those of
tan dm in the whole frequency range, which suggests that
microwave absorption enhancement of composite results
mainly from dielectric loss rather than magnetic loss.
Fig. 7 shows absorption characteristics of epoxy-BC
composite and epoxy-BC/Ag composites at the frequency
range of 18-40 GHz. Epoxy-BC composite achieves two
absorbing values of -14 and -11 dB at 18.2 and 31.5 GHz.
For epoxy-BC/Ag-1, -2 and -3 composites, their absorbing
values are -10.5 dB at 25 GHz, -4.5 dB at 25.5 GHz and
-2.8 dB at 25 GHz. The reflection losses of epoxy-BC/Ag
composites are found to depend on the sensitivity of the sil-
ver content. In comparison with the epoxy-BC sample, the
epoxy-BC/Ag composites showed that the attenuation
peaks decreased from -10.5 to -2.8 dB and shifted to lower
frequency from 31 to 25 GHz. This absorbing ability weak-
ening and frequency shift decrease can be attributed to the
fact that the addition of silver on the BC surface results in
Fig. 5. Microwave absorbing properties of epoxy-BC
and epoxy-BC/Ag composites in 2-18 GHz.
Bamboo Charcoal Coated with Silver (BC/Ag)
the surface reflectivity of composites as silver increases.19,20
And thus the epoxy-BC composite wouldnt result in a re-
markable improvement of the absorbing ability at 18-40
GHz.
Infrared thermal images
Before the experiment, the plate sample was placed
before the blackbody at 100 cm, in which the temperature
Fig. 6. Frequency dependences of the complex permittivity, complex permeability and dielectric/magnetic loss tangent of
epoxy-BC and epoxy-BC/Ag composites in 18-40 GHz.
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 729
was ~1000 C. Figs. 8(a) and (b) show the mid-wave infra-
red (3-5 mm) and long-wave infrared (8-12 mm) thermal im-
ages of the pure polyethylene, BC powders and BC/Ag-1,
-2 and -3 composites mixed with polyethylene (PE), re-
spectively. It can be seen from Fig. 8(a) that the surface
maximum temperature (700 C) was not decreased and av-
erage temperature decreased significantly for the polyeth-
ylene-BC (PE-BC, 360 C) and PE-BC/Ag-1 (351 C),
730 J. Chin. Chem. Soc., Vol. 55, No. 4, 2008
Fig. 7. Microwave absorbing properties of epoxy-BC
and epoxy-BC/Ag composites in 18-40 GHz.
Fig. 8. (a) The mid-wave infrared (3-5 mm) and (b)
long-wave infrared (8-12 mm) thermal images
of the PE, PE-BC and PE-BC/Ag composites.
The value in parentheses is the maximum and
average temperatures (C).
PE-BC/Ag-2 (340 C) and PE-BC/Ag-3 (330 C) compos-
ites in comparison with the value for the pure polyethylene
(488 C). From Fig. 8(b), the surface temperature (maxi-
mum and average) decreased significantly following the
increasing silver content of PE-BC/Ag-1, -2 and -3 com-
posites (118-110 C and 58-47 C) in comparison with the
value for the pure polyethylene (132 and 68 C). From the
above results it could be concluded that adding the silver to
the bamboo charcoal surface leads to higher infrared en-
ergy absorption and better shielding effect. We believe that,
after some more improvement, the thermal energy absorb-
ing and infrared shielding effects of the BC/Ag composites
could be further increased.
Ting et al.
CONCLUSION
In this work, bamboo charcoal/silver (BC/Ag) com-
posites were successfully prepared by the chemical reduc-
tion method. XRD, SEM and TEM studies have established
formation of BC/Ag composites. The complex relative
permittivity, permeability, loss tangent value and their rela-
tionship with microwave absorbing properties were inves-
tigated. It is found that the complex permittivity and loss
tangent value increase when the volume fraction of the sil-
ver particle increases, which results in microwave absorp-
tion properties in 2-18 and 18-40 GHz. The microwave ab-
sorption in 2-18 and 18-40 GHz of both epoxy-BC and ep-
oxy-BC/Ag composites results mainly from dielectric loss
rather than magnetic loss. It is obvious that epoxy-BC/Ag
composites increase performance of microwave absorbing
properties in 2-18 GHz. There is a little deterioration of the
microwave performance in 18-40 GHz, whereas the ab-
sorbing ability weakens in the low frequency before the ep-
oxy-BC peak frequency. In infrared image test results, ob-
servation of temperature differences for infrared energy ab-
sorption is determined in the 3-5 and 8-12 mm bands. In-
creasing silver on bamboo charcoal would effectively con-
tribute to the increase of infrared energy absorption. There-
fore, BC/Ag composite curtains mainly off infrared radia-
tion in the 3-5 and 8-12 mm bands.
ACKNOWLEDGEMENT
The authors thank the National Science Council of
the Republic of China for supporting this work (Grant NSC
96-2113-M-014-001). The authors wish to express their
gratitude to Mr. K. C. Wang of the NSC Instrument Center
for TEM analysis.
Received February 19, 2008.
REFERENCES
1. Pinho, M. S.; Gregori, M. L.; Reis Nunes, R. C.; Soares, B.
G. Polym. Degrad. Stab. 2001, 1, 73.
2. Knott, E. F.; Shaeffer, J. F.; Tuley, M. T. Rader Cross Sec-
tion; Artech House: New York, 1993; p 9.
3. Carvalho, A.; Gregori, M. L.; Chambers, B. Micro. Opt.
Tech. Lett. 1997, 16, 393.
4. Smith, F. C.; Chambers, B.; Bennett, J. C. IEE Proc. Sci.
Meas. Tech. 1994, 141, 538.
5. Petrov, V. M.; Gagulin, V. V. Inorg. Mater. 2001, 37, 93.
6. Liu, L. G.; Gong, R. G.; Cheng, Y. S.; Zhang, F. G.; He, H. H.
Opti. Exp. 2005, 13, 10382.
Bamboo Charcoal Coated with Silver (BC/Ag)
7. Bai, L. F.; Zhang, Y.; Zhang, C.; Qian, W. X.; Zhang, B. M.
Proc. Intell. Cont. Auto. 2006, 2, 10266.
8. Chen, S. W.; Wang, M. S.; Zhang, R. Enging. Med. Bio. Soc.
2005, 1-4, 1668.
9. Rogalski, A.; Chrzanowski, K. Opto-Electron. Rev. 2002,
10, 111.
10. Lars, G.; Karlsson, U. S. Patent. 4, 529, 633, 1985.
11. Tan, Z. H.; Tang, C. A.; Zhu, W. C. Key Enging. Mater.
2007, 353-358, 2313.
12. Xie, G. H.; Zhang, Z. G.; Wu, R. B. J. Wuhan Univ. Tech.
2005, 20, 55.
13. Ghodgaonkar, D. K.; Varadan, V. V.; Varadan, V. K. IEEE
Trans. Instrum. Meas. 1989, 37, 789.
14. Vinoy, K. J.; Jha, R. M. Radar Absorbing Materials; Kluwer
J. Chin. Chem. Soc., Vol. 55, No. 4, 2008 731
Academic Publishers: Boston, 1996; p 37.
15. Miki, M.; Kikuchi, T.; Nakamura, M.; Hatakeyama, K.;
Takada, J. Trans. Mater. Res. Soc. Jpn. 2003, 28, 1053.
16. Singjai, P.; Wongjamras, A.; Yu, L. D.; Tunkasiri, T. Chem.
Phys. Lett. 2002, 366, 51.
17. Khanna, P. K.; Singh, N.; Charan, S.; Viswanath, A. K. Ma-
ter. Chem. Phys. 2005, 92, 214.
18. Yue, Z. X.; Li, L. T.; Zhou, J.; Zhang, H. G.; Gui, Z. L. Mater.
Sci. Enging B. 1999, 64, 68.
19. Lee, B. Y.; Lee, J. W.; Yun, Y. C.; Jeong, I. B.; Moon, J. Ma-
ter. Sci. Forum. 2007, 534, 1449.
20. Peng, C. H.; Wang, H. W.; Kan, S. W.; Shen, M. Z.; Wei, Y.
M.; Chen, S. Y. J. Magn. Magn. Mater. 2004, 284, 113.