J Mater Sci (2014) 49:5199–5207

DOI 10.1007/s10853-014-8229-9

Microwave-absorbing properties of silver nanoparticle/carbon

nanotube hybrid nanocomposites
Gan Jet Hong Melvin • Qing-Qing Ni •

Yusuke Suzuki • Toshiaki Natsuki

Received: 28 November 2013 / Accepted: 5 April 2014 / Published online: 23 April 2014
Ó Springer Science+Business Media New York 2014

Abstract Silver (Ag) nanoparticles fabricated by chemi- than -10 dB (over 90 % absorption) was from 11.7 to
cal reduction process were grafted onto the surface of 14.0 GHz. The Ag/CNT hybrid nanocomposite with
carbon nanotubes (CNTs) to prepare hybrid nanocompos- thickness of 6 mm showed a minimum reflection loss of
ites. The Ag/CNT hybrid nanomaterials were characterized *-32.1 dB (over 99.9 % absorption) at 3.0 GHz and was
using transmission electron microscopy, X-ray photoelec- the best absorber when compared with the other samples of
tron spectroscopy, and Raman spectroscopy. The Ag/CNT different thickness. The reflection loss shifted to lower
hybrid nanomaterials were then loaded in paraffin wax, and frequency as the thickness of the samples increased. The
pressed into toroidal shape with thickness of 1 mm to capability to modulate the absorption band of these sam-
evaluate their complex permittivity and complex perme- ples to suit various applications in different frequency
ability by scattering parameters measurement method in bands simply by manipulating their thickness indicates that
reflection mode using vector network analyzer. The these hybrid nanocomposites could be a promising micro-
reflection loss of the samples was calculated according to wave absorber.
the transmission line theory using their measured complex
permittivity and permeability. The minimum reflection loss Keywords Microwave absorber  Silver nanoparticles 
of the Ag/CNT hybrid nanocomposite sample with a Carbon nanotubes  Reflection loss
thickness of 1 mm reached 21.9 dB (over 99 % absorption)
at 12.9 GHz, and also exhibited a wide response bandwidth
where the frequency bandwidth of the reflection loss of less Introduction

The advancement of electronic devices and communication

instruments in commercial, industrial, scientific, and mili-
G. J. H. Melvin tary fields, such as mobile phones, computers, radar tech-
Interdisciplinary Graduate School of Science and Technology, nology, and wireless network systems is progressing
Shinshu University, Tokida, Ueda 386-8576, Japan rapidly [1–4]. Although these technologies are convenient,
electromagnetic (EM) radiation has restricted their devel-
Q.-Q. Ni (&)  T. Natsuki
Department of Functional Machinery and Mechanics, Shinshu opment and is becoming a serious problem. EM radiation
University, Tokida, Ueda 386-8576, Japan can pollute the environment and harm the health of human
e-mail: [email protected] beings, especially expectant mothers and children [1–4].
Therefore, it is essential to protect electronic devices and
Q.-Q. Ni
Key Laboratory of Advanced Textile Materials and human beings from excessive exposure to EM radiation.
Manufacturing Technology, Ministry of Education, Zhejiang Microwave-absorbing materials have received much
Sci-Tech University, Hangzhou, China attention to effectively solve the problem of exposure to
EM radiation. An ideal microwave absorber should be
Y. Suzuki
Graduate School of Science and Technology, Shinshu lightweight, strongly absorb microwaves, and possess
University, Tokida, Ueda 386-8576, Japan tunable absorption frequency, and multifunctionality [1, 2].

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Nanomaterials such as nanoparticles and nanocompos- In this study, we prepare Ag nanoparticles and graft
ites are among important candidates as microwave- them onto the surface of CNTs. We then evaluate the
absorbing materials [5]. The relative density of nanoma- ability of these materials to absorb microwaves by mea-
terials is lower and their specific surface area is larger than suring their dielectric and/or magnetic losses when pene-
those of the corresponding bulk materials. As a result, there trated by an EM wave [1, 16]. The complex permittivity
are a large number of active atoms at the nanomaterial and complex permeability of these hybrid nanocomposites
surface, which has a large interfacial dielectric loss induced are measured, and their reflection loss is also evaluated.
by interface polarization [1]. Metal nanoparticles such as
silver (Ag) nanoparticles hybridized with carbon nanotubes
(CNTs) have potential to be developed as advanced
Experimental
materials for a wide range of applications [6–11], including
as microwave-absorbing materials [12, 13]. CNTs are light,
Modification of CNTs
possess a high aspect ratio and unique magnetic properties,
and exhibit favorable mechanical, chemical, and electric
CNTs can be modified with a single or mixture of acids
properties that have attracted considerable attention [2, 7–
[12, 13, 18]. Multi-walled CNTs (Wako Pure Chemical
9, 13–16]. Their high electrical conductivity makes CNTs
Industries Ltd., Japan, d = 40–70 nm) were functionalized
capable of dissipating electrostatic charges or shielding EM
by chemical oxidation in nitric acid (HNO3). The CNTs
radiation [16]. However, CNTs disperse poorly in organic
were heated under reflux in boiling HNO3 at 120 °C for
and aqueous solvents because of a strong intrinsic van der
10 h. The resulting mixture was centrifuged with pure
Waals attraction [11, 17]. Many techniques have been used
water, diluted with pure water, and left overnight until the
to solve the problem by functionalizing the CNTs using
pH was neutral. The CNTs were centrifuged again with
acid treatment [12, 13, 18], mild hydrothermal treatment
pure water to separate them, and then dried overnight at
[17], microwave-induced radical polymerization [19], and
60 °C. The acid-treated CNTs are denoted as modified
so on. In this study, we used acid treatment method to
CNTs hereafter. The samples for pristine CNTs were pre-
functionalize the CNTs. This treatment is fast, easy, and
pared by using obtained CNTs without any further
leads to the introduction of carboxyl and hydroxyl groups
modification.
to the surface of the CNTs, which allows them to be highly
dispersed in polar solvents. Furthermore, Ag is a good
conductor, abundant, easy to prepare, and inexpensive [9– Preparation of Ag nanoparticles
11]. Ag nanoparticles decoration would have a beneficial
effect on the electrical conductivity of CNTs because the Ag nanoparticles can be produced by chemical reduction,
inherent electrical conductivity of Ag is superior to the which only requires simple equipment and is convenient,
CNTs without Ag [9]. Metal nanoparticles such as Ag inexpensive, and gives a high yield [18, 20, 21]. The prepa-
nanoparticles, produced large electric or magnetic loss and ration is based on Ref. [20, 21], where method in Ref. [20] was
have been demonstrated to show promising microwave done by one of our research group. This method has advan-
absorption [1, 4]. Furthermore, metal nanoparticles such as tages including short reaction time; small and relatively
Ag nanoparticles decorated on the CNTs will absorb the uniform particles can be fabricated; the reaction proceeds
microwave energy through electrons hopping and shows rapidly at room temperature; high purity and good conduc-
enhanced microwave absorption bandwidth [2]. The com- tivity. Silver nitrate (AgNO3), sodium citrate (Na3Ct), and
bination of Ag nanoparticles with CNTs can integrate the 2-dimethylaminoethanol (DMAE) were obtained from Wako
properties of these two components to form hybrid nano- Pure Chemical Industries Ltd., Japan. Polyvinylpyrrolidone
composites for use as microwave-absorbing materials. (PVP, K 15, Tokyo Chemical Industry Co. Ltd., Japan) was
Reports on Ag nanoparticles or Ag/CNT hybrid mate- used to prevent aggregation of the Ag nanoparticles.
rials as microwave absorbers are very limited. Ramesh PVP (1.0 g) was stirred in pure water (20 mL) for
et al. [4] investigated the microwave-absorbing properties 10 min. AgNO3 (0.5 g) was added, and the mixture was
of Ag nanoparticles embedded in thin polymer films. stirred vigorously for 10 min. Na3Ct (0.88 g) diluted in
Meanwhile, Zhao et al. [12, 13] investigated the micro- pure water (20 mL) was added dropwise to the stirred
wave-absorbing properties of CNTs filled with Ag nano- mixture. Then, DMAE (0.03 g) was added and the mixture
wires. To the best of our knowledge, the microwave- was stirred for 1 h. Finally, the mixture was centrifuged,
absorbing properties of Ag/CNT hybrid nanocomposites washed with pure water, and dispersed in ethanol (10 mL).
where Ag nanoparticles are decorated on the surface of The Ag nanoparticles dispersed in ethanol (solution A)
CNTs have not been examined. were used to prepare Ag/CNT hybrid nanocomposites.

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Preparation of Ag/CNT hybrid nanocomposites Results and discussion

Ag nanoparticles were grafted onto the surface of the CNTs Morphology of Ag/CNT hybrid nanocomposites
according to the method reported in Ref. [18] with some
modification. Cysteamine hydrochloride and 2,5-dihy- TEM images of the Ag nanoparticles, modified CNTs and
droxybenzoic acid (DHB) obtained from Wako Pure Ag/CNT hybrid nanocomposites are depicted in Fig. 1.
Chemical Industries Ltd., Japan, were used to link the Ag Figure 1a, b show that the Ag nanoparticles had diameters
nanoparticles to the surface of the CNTs. of less than 10 nm, ranging from 5 to 10 nm. Figure 1c
Ag nanoparticles in ethanol (5 mL, obtained from shows the modified CNTs before Ag nanoparticles were
solution A) were sonicated for 10 min, and then reacted grafted on their surfaces. The diameter of the CNTs was
with cysteamine hydrochloride (0.23 g) in ethanol (95 mL) about 40 nm, and they contained some defects on their
at 80 °C for 6 h in an oil bath (mixture A). The total walls after modification by acid treatment. Figure 1d, e, f
volume of mixture A was 100 mL. At the same time, show TEM images of the Ag/CNT hybrid nanocomposites
modified CNTs (0.05 g) were sonicated in ethanol with Ag nanoparticles grafted onto the surface of the
(100 mL) for 1 h (mixture B). DHB (0.08 g) was added to CNTs. Ag nanoparticles were homogeneously dispersed
mixture B, which was then sonicated for 30 min. Mixture with no agglomeration and strongly adhered to the surfaces
A and B were combined, and then stirred for 24 h. The of the CNTs. The diameter of the Ag nanoparticles grafted
resulting product was centrifuged, washed with pure water, onto the surface of the CNTs was also less than 10 nm.
and then dried overnight at 60 °C.
XPS analysis of Ag/CNT hybrid nanocomposites
Evaluation methods
XPS evaluation was carried out to determine the elemental
Transmission electron microscopy (TEM) images of the Ag composition and functional groups of the pristine CNTs,
nanoparticles, modified CNTs, and Ag/CNT hybrid modified CNTs, and Ag/CNT hybrid nanocomposites, as
nanomaterials were obtained using a TEM (JEM-2100, shown in Fig. 2. The pristine and modified CNTs exhibited
JOEL, Japan) with an accelerating voltage of 200 kV. a strong carbon (C 1s) peak at 284 eV and oxygen (O 1s)
X-ray photoelectron spectroscopy (XPS, Kratos Axis Ultra peak at 532 eV. The modified CNTs clearly showed an O
DLD) was performed with a standard Mg Ka (1256.6 eV) 1s peak with higher intensity than that of the pristine
X-ray source operating at 10 mA and 15 kV to characterize CNTs. The atomic percentage ratios for the pristine CNTs
the elemental composition and chemical states of the are 98.59 % for C 1s and 1.41 % for O 1s, while those of
samples. Raman spectroscopy measurements were per- the modified CNTs are 92.40 % for C 1s and 7.60 % for O
formed on a Raman spectrometer (HoloLab series 5000, 1s. The higher intensity of the O 1s peak confirms that
Kaiser Optical Systems) with 532-nm laser excitation. many oxygen functional groups (carboxyl and hydroxyl)
The real and imaginary parts of complex permittivity e were introduced onto the surface of the CNTs modified by
(e = e0 – je00 ) and permeability l (l = l0 – jl00 ) were acid treatment.
measured by scattering parameters measurement method in The XPS survey spectrum of the Ag/CNT hybrid
reflection mode using a vector network analyzer (37247D, nanomaterial confirmed the presence of C 1s, O 1s, nitro-
Anritsu Co. Ltd.) within the frequency range of gen (N 1s), chlorine (Cl 2p3/2), silver (Ag 3d, Ag 3p), and
0.5–14 GHz. Samples for these measurements were pre- sulfur (S 2s, S 2p). The Ag/CNT samples showed a strong
pared by loading the Ag/CNT hybrid nanocomposites in C 1s peak at 284 eV, O 1s peak at 531 eV, N 1s peak at
paraffin wax with a weight percentage of Ag/CNT hybrid 400 eV, and Cl 2p3/2 peak at 198 eV. Ag 3d peaks from Ag
nanocomposite to paraffin of 30 %. The complex permit- 3d5/2 and Ag 3d3/2 appeared at 368 and 374 eV, respec-
tivity and permeability of the paraffin wax are low and tively. Ag 3p peaks from Ag 3p3/2 and Ag 3p1/2 were
constant throughout the frequency range [12]. Furthermore, observed at 573 and 604 eV, respectively. The S 2s and S
the paraffin wax shows almost no absorption. The powder- 2p peaks appeared at 227 and 163 eV, respectively. The
wax composites were pressed into a toroidal shape using a presence of Ag 3d and Ag 3p peaks proves the formation of
mold designed with an outer diameter of 7 mm, inner Ag nanoparticles. Furthermore, the observation of N 1s, Cl
diameter of 3 mm, and thickness of 1 mm. The thickness 2p3/2, S 2s, S 2p, Ag 3d, and Ag 3p peaks confirmed that
was also measured using vernier caliper to check the uni- the amidation reaction between cysteamine hydrochloride
formity. The reflection loss was calculated from the mea- (NH2(CH2)2SHHCl) and Ag nanoparticles was successful
sured complex permittivity and permeability of the [18]. The CNTs were oxidized using acid treatment in
samples. order to introduce carboxyl and hydroxyl groups onto the

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Fig. 1 TEM images of a, b Ag nanoparticles; c modified CNTs; d, e, and f Ag/CNT hybrid nanocomposites

Fig. 3 XPS of the Ag 3d core level of the Ag/CNT hybrid

nanocomposites

surface of CNTs. Ag nanoparticles were modified with

self-assembled monolayers cysteamine hydrochloride,
resulting in cysteamine hydrochloride-Ag groups. Using
DHB as a coupling agent, the modified CNTs functional-
ized with carboxyl and hydroxyl groups on the surface
reacted with the amino groups on the silver surface through
amide bonds [18]. The Ag 3d doublet peaks with separation
Fig. 2 XPS spectra of pristine CNTs, modified CNTs, and Ag/CNT energy of 6 eV shown in Fig. 3 are consistent with Ag
hybrid nanocomposites metal, further confirming that Ag on the surface of the

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Fig. 5 Relative intensity ratios of D/G, G0 /G, and G0 /D peaks of

Fig. 4 Raman spectra of pristine CNTs, modified CNTs, and Ag/ pristine CNTs, modified CNTs, and Ag/CNT hybrid nanocomposites
CNT hybrid nanocomposites

relative intensities of the D/G, G0 /G, and G0 /D ratios are

CNTs exists in the zero-valent state [7, 8, 18]. The atomic presented in Fig. 5. The D/G ratio is 0.94, 1.07, and 1.11
percentage ratios for the Ag/CNT nanomaterials are for the pristine CNTs, modified CNTs, and Ag/CNT hybrid
87.02 % for C 1s, 7.04 % for O 1s, 2.73 % for Ag 3d, and nanocomposites, respectively. The increase of the D/G
3.22 % for Ag 3p. ratio of the modified CNTs compared with that of the
pristine CNTs confirms the successful introduction of
Raman spectroscopy of Ag/CNT hybrid functional groups onto the CNTs surface and that the outer
nanocomposites layers of the CNTs were chemically modified [17, 19]. The
slight increase between the D/G ratio of the modified CNTs
Raman spectroscopy is an effective tool to characterize and that of the Ag/CNT hybrid nanocomposites can be
carbon-based materials [17, 19, 22–24], so Raman spectra attributed to the introduction of Ag nanoparticles onto the
of the pristine CNTs, modified CNTs, and Ag/CNT hybrid surface of the CNTs. The G0 /G ratio is 0.86, 0.82, and 0.67
nanocomposites were measured. The characteristic bands for the pristine CNTs, modified CNTs, and Ag/CNT hybrid
of CNTs, D band (defect) at *1350 cm-1, G band nanocomposites, respectively. Moreover, the G0 /D ratio is
(graphite band) at *1580 cm-1, and G0 band (D overtone) 0.92, 0.77, and 0.60 for the pristine CNTs, modified CNTs,
at *2700 cm-1 were observed, as illustrated in Fig. 4. The and Ag/CNT hybrid nanocomposites, respectively. The
D0 band of the modified CNTs and Ag/CNT hybrid nano- decrease of the G0 /G and G0 /D ratios of the modified CNTs
composites ranging from 1600 to 1620 cm-1, which is compared with those of the pristine CNTs reveals a higher
attributed to structural defects and broadened caused by density of lattice defects in the acid-treated CNTs [22]. A
modification with Ag [24], was also observed. For the Ag/ decrease of the intensity of the G0 peak of the Ag/CNT
CNT hybrid nanocomposites, the G0 peak shifted to higher hybrid nanocomposites (Fig. 4) as the mass fraction of
wavenumber, *2688 cm-1 (pristine CNTs: *2679 cm-1, CNTs in the hybrid material decreases is also clear. The G0
modified CNTs: *2680 cm-1), because of a substantial peak arises from a two-phonon process, so it is reasonable
charge transfer interaction between the Ag nanoparticles that its intensity decreases as the sample becomes less
and CNTs [24]. ordered (i.e., more impurities or introduced surface spe-
The relative intensity of the D and G bands (ID/IG) is cies), not allowing for the coupling effect that is required
related to the amount of structural defects and sp3- for the two-phonon process [25]. The G0 /G and G0 /D ratios
hybridized carbon atoms in a CNT sample, and thus pro- of the Ag/CNT hybrid nanocomposites showed the lowest
vides direct information about the degree of sidewall values because the CNTs were sonicated before being
functionalization [19, 22]. Furthermore, the relative inten- attached with Ag nanoparticles, which promotes the for-
sity of the G0 and G bands (IG0 /IG) and the relative intensity mation of structural defects. Attachment of Ag nanoparti-
of the G0 and D bands (IG0 /ID), which are related to the cles could also cause the G0 /G and G0 /D ratios to decrease
scale on which the graphitic order extends and the degree through the interaction between the Ag nanoparticles and
of crystallinity [22], respectively, were also evaluated. The CNTs.

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Fig. 6 Complex permittivity of the modified CNT composite Fig. 7 Complex permeability of the modified CNT composite
(t = 1 mm) and Ag/CNT hybrid nanocomposite (t = 1 mm). (t = 1 mm) and Ag/CNT hybrid nanocomposite (t = 1 mm).
a Real part permittivity, and b imaginary part permittivity a Real part permeability, and b imaginary part permeability

Electromagnetic wave absorption properties permittivity of the Ag/CNT hybrid nanocomposites can be
attributed to the multiple interfacial polarizations between
Complex permittivity and complex permeability are basic the Ag nanoparticles, CNTs, and paraffin wax [27]. Fur-
parameters associated with the microwave absorption thermore, the polarization mainly contains thermal ion
properties of a material, where the real parts of complex polarization, dipole rotation polarization, electronic dis-
permittivity and permeability represent the storage of placement polarization, ion polarization, and so on [1]. The
electric and magnetic energies, respectively, while the time for electronic displacement and ion polarization is very
imaginary parts symbolize the loss and dissipation of both short, thus these polarizations produce energy loss at high
energies [1, 2]. The complex permittivity (real part e0 and frequency region [1].
imaginary part e00 ) of the modified CNT composite (thick- The complex permeability (real part l0 , imaginary part
00
ness, t = 1 mm) and Ag/CNT composite (t = 1 mm) loa- l ) of the modified CNTs composite (t = 1 mm) and Ag/
ded in paraffin wax in the range of 0.5–14 GHz is presented CNT hybrid nanocomposite (t = 1 mm) in the range of
in Fig. 6. As the frequency increased, the complex per- 0.5–14 GHz is shown in Fig. 7. Interestingly, the presence
mittivity decreased because the polarizabilities (electronic, of Ag nanoparticles affected the complex permeability of
ionic, and orientation) and electric displacement are not the hybrid nanocomposites. l0 of the Ag/CNT hybrid
maintained in a changing EM field [26, 27]. The modified nanocomposite was higher than that of the modified CNT
CNTs composite exhibited higher complex permittivity composite, and increased until a certain frequency, after
than the Ag/CNT hybrid nanocomposite. This can be which it gradually decreased. This can be attributed to
explained by the high electrical conductivity of the CNTs natural resonance or eddy current loss [1, 27]. When Ag
that enables strong polarization to occur, Ohmic losses, (conducting material) was put in an alternating magnetic
dissipation of electrostatic charges, or multiple scattering field, a close induced current will be produced inside
caused by the large specific area, which lead to improved the material, which would dissipate the energy and referred
complex permittivity [2, 16]. The behavior of the complex as eddy current loss [1]. Both Ag and CNTs possess

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Fig. 9 Reflection loss of the modified CNT composite (t = 1 mm)

Fig. 8 Dielectric loss factor and magnetic loss factor of the Ag/CNT and Ag/CNT hybrid nanocomposite (t = 1 mm) in the range of
hybrid nanocomposite with t = 1 mm 0.5–14 GHz

high electrical conductivity. This leads to permeability rffiffiffiffiffi   

lr 2pfd pffiffiffiffiffiffiffiffi
decreasing rapidly at high frequency caused by the eddy Zin ¼ tanh j lr er ð2Þ
er c
current loss. The strong attenuation of permeability with
increasing frequency is due to the screening of the elec- where er = e0 - je00 , lr = l0 - jl00 , f is the microwave
tromagnetic field by eddy currents [28]. This reduces the frequency (Hz), d is the thickness of the absorber (m), and
initial permeability and introduces a typical decaying c is the velocity of light in free space (m/s). R.L. of the
envelope in the intrinsic permeability signal [28]. When a modified CNT composite with t = 1 mm and the Ag/CNT
composite is exposed to a changing EM field, the Lorentz hybrid nanocomposites with t = 1 mm are shown in
force on the electrons in the Ag nanoparticles provokes Fig. 9.
them to circulate, producing eddy currents [27]. A mag- The Ag/CNT hybrid nanocomposite with t = 1 mm
netic field induced by the eddy currents that opposes the showed a minimum R.L. of *-21.9 dB (over 99 %
applied field causes the composites to radiate an EM wave, absorption) at 12.9 GHz. Furthermore, this sample also
which increases the total magnetic energy and results in exhibited a wide response bandwidth of 2.3 GHz, where
decreased permeability [15, 27]. the frequency bandwidth (R.L. of less than -10 dB, over
To reveal the intrinsic reasons for the microwave 90 % absorption) is from 11.7 to 14.0 GHz. Conversely,
absorption by the Ag/CNT hybrid nanocomposites, their the modified CNT composite with t = 1 mm showed a
dielectric loss factor (tan de = e00 /e0 ) and magnetic loss factor minimum R.L. of *-14.1 dB at 13.5 GHz with a response
(tan dl = l00 /l0 ) were evaluated. Figure 8 presents tan de and bandwidth of 2.0 GHz (12.0–14.0 GHz). The peak of the
tan dl of the Ag/CNT hybrid nanocomposite with t = 1 mm. minimum R.L. shifted to lower frequency for the Ag/CNT
The relaxation observed from tan de can be attributed from hybrid nanocomposite compared with that of the modified
energy loss in the materials illuminated by electromagnetic CNT composite of similar thickness. Moreover, R.L. and
field comes about through damping forces acting on polar- the response bandwidth of the Ag/CNT hybrid nanocom-
ized atoms and molecules and trough the finite conductivity posite are both superior to the equivalent values of the
of the materials [2]. Both tan de and tan dl contribute to the modified CNT composite. Even though the modified CNT
microwave absorption; in the low frequency region, tan de is composite exhibited higher complex permittivity and
sensitive to microwaves; and at high frequency, tan dl is complex permeability, the Ag/CNT hybrid nanocomposite
sensitive to microwaves. was the better absorber because it showed a higher mini-
To investigate the microwave absorption properties of mum R.L. According to Ref. [1, 2], suitable complex per-
the samples, the reflection loss (R.L.) was calculated mittivity and complex permeability are essential to
according to the transmission line theory as follows: promote EM wave absorption. This also can be related to
  another important parameter connected to R.L., i.e., the
Zin  1
R:L: = 20 log  ; ð1Þ concept of matched impedance. This concept suggests that
Z þ 1
in
the characteristic impedance of an absorber should be
where the normalized input impedance (Zin) is given by the almost equal to that of the free space to achieve zero
formula, reflection on the front surface of the material [29–31].

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the minimum R.L. (highest absorption) of the Ag/CNT

hybrid nanocomposites can be controlled by changing the
thickness of the sample. Furthermore, absorption at low and
high frequency region also can be archived by changing the
thickness of Ag/CNT hybrid nanocomposites. We believe
that the Ag/CNT hybrid nanocomposites are a promising
microwave absorber, because their absorption band can be
modulated simply by manipulating the sample thickness to
satisfy applications in different frequency bands.

Conclusions
Fig. 10 Reflection loss of the Ag/CNT hybrid nanocomposite (t = 2,
3, 4, 5, 6, and 7 mm) in the range of 0.5–14 GHz Ag nanoparticles were grafted onto the surface of CNTs to
fabricate Ag/CNT hybrid nanomaterials. TEM, XPS, and
Raman spectroscopy analyses revealed the morphology,
Obviously, to design an optimized absorber with a high structure, and elemental composition of the hybrid
minimum R.L., appropriate EM impedance matching is nanomaterials. The Ag nanoparticles were less than 10 nm
important. in diameter and showed no agglomeration when adhered to
There are many boundaries in the Ag/CNT hybrid the surface of CNTs. The high interfacial area of the hybrid
nanocomposites, including between the Ag surfaces, CNT nanomaterials results in high interfacial polarization and
surfaces, and paraffin wax. Moreover, because the CNTs multiple scattering, which improves microwave absorption.
were modified both prior to and during the process of Ag The Ag/CNT hybrid nanomaterials exhibited a minimum
nanoparticle coating, the Ag/CNT hybrid nanocomposites R.L. of 21.9 dB (over 99 % absorption) at 12.9 GHz with a
contain many defects and suspended bonds, as shown in the wide response bandwidth (2.3 GHz), superior than the
Raman spectra of the samples (Figs. 4, 5). As a result, the modified CNT composite with same thickness of 1 mm.
large specific areas of the surfaces of the hybrid nano- Furthermore, the Ag/CNT hybrid nanomaterials, t = 6 mm
composites triggered higher interfacial polarization and showed a minimum R.L. of *-32.1 dB (over 99.9 %
multiple scattering, which leads to a high minimum R.L.. absorption) at 3.0 GHz and was the best absorber when
Interfacial multipoles contribute to the strong EM wave compared with the other samples of different thickness.
absorption of the hybrid nanocomposites. The Ag/CNT hybrid nanomaterials showed two R.L. peaks,
According to Eq. (2), the thickness of the absorber can at low and high frequency region, as the thickness of the
also affect R.L., so we investigated the relationship between sample increased. They also showed wide minimum R.L. of
the thickness and R.L. of the Ag/CNT hybrid nanocompos- over -10 dB (over 90 % absorption). This proves that the
ites. R.L. for Ag/CNT hybrid nanocomposites with t = 2, 3, thickness of samples can be manipulated to produce
4, 5, 6, and 7 mm was calculated and shown in Fig. 10. absorption bands at different frequencies to design highly
When the thickness of the Ag/CNT hybrid nanocomposite effective microwave absorbers.
increased, the frequency of the R.L. peak decreased. When
t = 3 mm and above, extra peak was observed at lower Acknowledgements This work was supported by Grants for
Excellent Graduate Schools by the Ministry of Education, Culture,
frequency region, between 0.5 to 9.0 GHz. The R.L. peaks at
Sports, Science and Technology, Japan.
higher frequency showed over 90 % absorption ([10 dB)
meanwhile, the R.L. peaks at lower frequency showed over
99 % absorption ([20 dB). As the thickness increased
beyond t = 3 mm, the R.L. peak (response bandwidth) at
high frequency region become broader; and R.L. peak at low References
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