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Synthetic Metals 158 (2008) 251258

Synthesis, characterization and microwave absorption property of doped polyaniline nanocomposites containing TiO2 nanoparticles and carbon nanotubes
Sook Wai Phang a , Masato Tadokoro b , Jiro Watanabe b , Noriyuki Kuramoto a,
a

Graduate Program of Human Sensing and Functional Sensor Engineering, Graduate School of Science and Engineering, Yamagata University, 4-3-16 Jonan, Yonezawa, Yamagata 992-8510, Japan b The Yokohama Rubber Co. Ltd., 2-1 Oiwake, Hiratsuka-Shi, Kanagawa-Ken 254-8601, Japan Received 7 September 2007; received in revised form 22 November 2007; accepted 24 January 2008 Available online 11 March 2008

Abstract As nanomaterial possessing moderate conductivity, magnetic and dielectric property, novel hexanoic acid (HA)-doped polyaniline (PAni) nanocomposites containing TiO2 nanoparticles (dielectric ller) and carbon nanotubes, CNTs (magnetic llers such as single-walled carbon nanotube, SWNT and multi-walled carbon nanotube, MWNT) were prepared by template free method. The PAni were characterized by UV, FTIR, X-ray diffraction (XRD), thermogravimetric (TGA) and scanning electron microscopy (SEM) analyses. Conductivity, magnetization, dielectric and microwave absorption properties of PAni were also investigated. The resulted nanorods/tubes as shown in SEM images clearly show that polymerization is proceeded in micelle/water interface through elongation. During template free method, TiO2 and CNT exist in the center of Ani/HA micelle. The SEM images show that some of the CNT enwrapped with PAni layer indicate CNT are just packed underneath the PAni and never attacked by PAni. PAni/HA/TiO2 /SWNT with 20% of SWNT exhibits the best microwave absorption property (99.2% absorption) with reection loss of 21.7 dB at 6 GHz due to its moderate conductivity (1.27 S/cm), magnetization (Ms = 1.01 emu/g), highest tan and heterogeneity. 2008 Elsevier B.V. All rights reserved.
Keywords: Polyaniline; Nanocomposites; TiO2 ; Carbon nanotube; Conductivity; Microwave absorption property

1. Introduction Rapid development in space technology, telecommunication and rapid proliferation of electronic devices over the past few decades has increased the vulnerability to electromagnetic interference (EMI) [1]. High conductivity, dielectric permittivity and magnetic permeability of the materials contribute to high EMI shielding efciency [2]. Traditional microwave shielding and absorbing materials such as metals and magnetic materials possess good mechanical and shielding property but display disadvantages such as heavy, corrosive and poor processibility. Metals cannot be used as electromagnetic (EM) wave absorbers since their shallow skin depth make them shield EMI mainly through the surface reection

Corresponding author. Tel.: +81 238 26 3051; fax: +81 238 26 3051. E-mail address: kuramoto@yz.yamagata-u.ac.jp (N. Kuramoto).

[3]. Conductive polymers are widely studied for this application because of their foremost properties such as high conductivity to weight ratio, corrosion resistant and facile processibility [47]. Conducting polymers exhibit special properties compared to metals in the sense that they do not only reect but also selectively absorb electromagnetic radiations [8]. Various conductivities with radiation frequency have made them useful in radar absorbing materials [9]. Nowadays, micro/nanowires have attracted considerable attention because of their unique properties and potential applications in nanodevices [1014]. Conducting polymer as molecular wires is an excellent choice because of their long -conjugation length as well as their high metal conductivity [15]. Among conducting polymers, polyaniline (PAni) is perhaps the most versatile because of their desirable properties, such as thermal and chemical stability, controllable conductivity and high conductivity at microwave frequencies [16,17]. PAni can be exploited in many applications such as microwave absorb-

0379-6779/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.synthmet.2008.01.012

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ing and shielding materials, microporous electrically conducting materials, supporting material for catalyst, etc. [11]. Combination of PAni with other organic or inorganic materials could yield new functional materials which enhance not only the mechanical property but also other properties depend on the additives used [18]. Tan and co-workers fabricated solid-state dye-sensitized TiO2 solar cells by using PAni as a hole-transport [19]. Regarding inorganic materials, crystalline TiO2 nanoparticles and carbon nanotubes are non-toxicity and chemical inertness that lead to broad applications in the elds of electronic, photonic and stealth technology. Recently, PAni/HCl/TiO2 nanocomposite was also reported by Dey et al. to show a large dielectric constant [20]. Single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT) are prospective llers that possess moderate magnetizations (Ms ) such as 3.142 and 4.998 emu/g, respectively (Table 1). These magnetizations were measured by vibrating sample magnetometer before polymerization process. Carbon nanotube (CNT) represents the youngest allotropic form of carbon having a high degree of constitutional organization. The high degree of organization and high respect ratio are responsible for their unique electric, magnetic and mechanical properties [21]. SWNT is seamless, hollow tubes of graphite with fullerence-like ends, while MWNT consists of many concentric SWNT [22]. Several studies regarding the synthesis of PAni/CNT nanocomposites that exhibited enhanced electrical, thermal or mechanical properties have been reported elsewhere [2224]. By incorporation of the dielectric and magnetic llers, the values of dielectric permittivity and magnetic permeability of such materials can be altered to achieve maximum absorption of the electromagnetic energy. Hence, PAni/Dopant/TiO2 /CNT nanocomposite should be an excellent microwave absorbing and shielding material because TiO2 and CNT are the dielectric and magnetic llers that could enhance the dielectric and magnetic properties of PAni. Besides that, hexanoic acid (HA) is the dopant used to improve the conductivity of PAni. However, the preparation and characterization of such composite have not reported yet. In this study, novel PAni nanocomposites were prepared by using CNT (SWNT and MWNT) as magnetic ller, TiO2 as dielectric ller and HA as dopant through template free method in order to develop PAni nanocomposites that could exhibit better magnetic, dielectric and conductivity behaviors. Template free method is commonly used to synthesize nanotubes of conducting polymers because the micelle consists of dopant or dopant/aniline salt could act as a soft template in the formation of PAni nanostructure [25]. Thermal stability, morphology, UV, FTIR, X-ray diffraction (XRD) characterizations, conductivity, magnetic, dielectric and microwave absorption behaviors of the nanocomposites are discussed in this report. 2. Experimental and characterization Aniline (Ani), n-hexanoic acid (HA), methanol and ammonium peroxydisulfate (APS) were purchased from Kanto Chemicals. TiO2 (anatase form) with particle size of 30 nm was

ordered from Tayca Corporation. SWNT (purity = 7090%) and MWNT (purity >90%) with diameter less than 10 nm were purchased from MTR Corporation, Japan and NTP Corporation, China, respectively. Water used for polymerization was puried by distillation. Other reagents were used as received. Firstly, HA (10 mmol) and Ani (10 mmol) were dissolved in distilled water (75 mL) and stirred vigorously for 30 min. 10% of TiO2 (0.10 g) and 10% of SWNT (0.10 g) were dispersed well in Ani/HA mixture under ultrasonic action for 12 h. APS solution (2.282 g, 25 mL) was then slowly added into the mixture. The Ani/HA/TiO2 /SWNT mixture was then polymerized for 24 h at 0 C under undisturbed state. PAni/HA, PAni/HA/TiO2 , PAni/HA/TiO2 /MWNT, PAni/HA/SWNT and PAni/HA/MWNT with different CNT contents (10, 20 and 60%) were synthesized using same preparation method. Finally, the nanocomposites were washed by distilled water and methanol three times, respectively. The nanocomposites were then characterized by FTIR, UV, X-ray diffraction, thermogravimetric (TGA) and scanning electron microscopy (SEM) analyses. FTIR measurements of PAni in KBr pellets were taken by using Shimadzu FTIR (model 8100 M) spectrometer from 400 to 4000 cm1 . UVvis absorption spectra of PAni methanol solutions were studied by JASCO UV/vis/near-IR spectrophotometer (model V-570) in the range of 3001000 nm. The PAnimethanol solution is mixed under ultrasonic action for 34 h before UV measurement. Hence, the solution is assumed as homogeneous solution. X-ray diffraction patterns of PAni were recorded by wide-angle goniometer with Cu K radiation from 3 to 60 . Thermograms of PAnis were recorded by Mettler-Toledo 851 thermogravimetric analyzer, in the presence of N2 atmosphere from room temperature to 600 C with a heating rate of 10 C/min. Morphology behaviors of PAni were determined from SEM (model JSM-6300F). Conductivities of the samples with compacted density of 1.1 g/cm3 were tested using a standard four-probe method (model Loresta HP). Magnetizations of the samples (magnetic eld from 10 to 10 kOe) were tested by vibrating sample magnetometer (model 1660). Microwave absorption properties of PAni nanocomposites were measured using microwave vector network analyzer Anritsu 37369C from 1 to 18 GHz. 3. Results and discussion FTIR spectra of PAni/HA/TiO2 , PAni/HA/TiO2 /CNT and PAni/HA/CNT indicate the peaks are derived from PAni/HA [25]. The stretching of CH3 and CH2 at 2933 and 2866 cm1 as well as the vibration mode of C O at 1755 cm1 are corresponding to the HA dopant [25]. The characterization peaks of CNT at 2937 and 1703 cm1 are due to the carbonyl stretching vibration and the CH stretching vibration [23]. The X-ray diffraction patterns indicate that PAni/HA shows amorphous behavior with three major peaks for the characterization of doped-PAni [25]. Besides that, XRD patterns of all PAni/HA/TiO2 /CNT clearly show the existence of TiO2 [26,27] and CNT [23]. UV spectra of PAni nanocomposites show the presence of peaks at 375381 nm ( * transition of benzenoid ring) and shoulder-like peak near 800 nm (conducting emeraldine salt of

S.W. Phang et al. / Synthetic Metals 158 (2008) 251258 Table 1 Conductivity and magnetization of CNT, PAni/HA/CNT and PAni/HA/TiO2 /CNT with different SWNT contents Conductivity (S/cm) (1) MWNT (2) SWNT (3) PAni/HA (4) PAni/HA/TiO2 (5) PAni/HA/MWNT (6) PAni/HA/SWNT (7) PAni/HA/TiO2 /MWNT (8) Pani/HA/TiO2 /SWNT 10% (9) PAni/HA/TiO2 /SWNT 20% (10) PAni/HA/TiO2 /SWNT 60% 1.88 104 1.62 106 6.01 102 4.81 102 5.85 103 6.60 102 1.27 101 7.15 100 Ms (emu/g) 4.998 3.142 8.44 101 5.64 101 6.00 101 5.76 101 1.01 1.70 Mr (emu/g) 7.131 101 7.70 101 1.34 101 5.47 102 1.34 101 2.46 101 4.14 101 4.483 101

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Hc (Oe) 41.81 156.9 42.6 177 41.9 179 180 180

PAni) [25]. It can be proposed that there is no chemical interaction between PAni/HA with TiO2 and CNT because there is no new peak formed in FTIR, UV and XRD spectra for all PAni nanocomposites. Thus, TiO2 and CNT are just physically mixed with PAni/HA. From the TGA proles, thermal stabilities of PAni nanocomposites are signicantly improved by the addition of TiO2 and CNT [2830]. Figs. 15 are SEM images of PAni nanocomposites prepared in this study. Refer to the proposed micelle mechanism of PAni/HA/TiO2 nanorods/tubes in Fig. 1(a), TiO2 nanoparticles are believed to exist in the center of Ani/HA micelles during polymerization. In this communication, it is believed that TiO2 and CNT are dispersed well in Ani/HA mixture because Ani/HA/TiO2 /CNT mixture is stirred vigorously under sonication for 12 h before polymerization. Ani is assigned as shell of micelle due to the hydrophobility of Ani and HA is acted as tail of micelle due to the hydrophilicity of COOH of HA dopant. Since there is a repulsive interaction of the tail group of micelle, thus the micelles exist as a uid surface and spherical micelles are expected to form through aggregation due to the lowest surface energy. After that, the Ani/HA micelles become big sphere by accretion or tubes/rods by elongation depends on the synthesis conditions. Polymerization of PAni nanocomposites is proceeded in the micelle/water interface due to the hydrophilicity of APS [14]. PAni/HA/TiO2 nanorods/tubes as shown in Fig. 1(c) indicate that Ani/HA micelle exhibits polymerization through elongation at the micelle/water interface. The mechanism that proposed here is well-agreed with the Ani/salicylic acid/TiO2 micelle mechanism that reported by Zhang et al. [14]. Big spheres that consist of smaller balls as shown in Fig. 1(b) indicate that Ani/HA micelle of PAni/HA (without TiO2 as nucleus) exhibits polymerization through accretion at the micelle/water interface. Based on the results above, it can be proved that the morphology behaviors (formation of nanorods/tubes and big spheres) of PAni nanocomposites are signicantly affected by the synthesis parameters such as the use of TiO2 as dielectric ller. Fig. 2(a) and (b) shows the micelle mechanisms of PAni/HA/CNT and PAni/HA/TiO2 /CNT nanocomposites. As shown by proposed micelle mechanism of PAni/HA/CNT and PAni/HA/TiO2 /CNT nanorods/tubes in Fig. 2(a), CNT and

TiO2 are believed to exist in the center of Ani/HA micelles during polymerization. The circled portion of PAni/HA/CNT and PAni/HA/TiO2 /CNT nanorods/tubes, marked as (b) in SEM images in Figs. 3(a) and 4(a), respectively are enlarged (60,000) and shown in Figs. 3(b) and 4(b). The resulted PAni/HA/CNT and PAni/HA/TiO2 /CNT nanorods/tubes in Figs. 3(b) and 4(b) clearly indicate that Ani/HA micelle (CNT and TiO2 as nucleus) exhibits polymerization through elongation at the micelle/water interface. During polymerization reaction, Ani/HA micelle without TiO2 or CNT as nucleus act as a soft-templates in the formation of nanostructure. However, Ani/HA micelle with TiO2 or CNT as nucleus might act as a hard templates since TiO2 or CNT is insoluble in the reaction solution. Besides the formation of PAni/HA/CNT and PAni/HA/TiO2 /CNT nanorods/tubes, some of the CNTs are covered by PAni/HA layers during in situ polymerization as shown by the proposed mechanism of rough CNT bers in Fig. 2(b). CNTs are just physically mixed or packed by PAni/HA layer during polymerization. This is similar as the proposed mechanism that reported by Feng et al. [23]. Feng et al. indicated that CNT are just packed underneath the PAni and never attacked by PAni during in situ polymerization. The circled portion of rough PAni/HA/CNT and PAni/HA/TiO2 /CNT bers, marked as (c) in SEM images in Figs. 3(a) and 4(a), respectively are enlarged (60,000) and shown in Figs. 3(c) and 4(c). Fig. 5 is the SEM images of PAni/HA/TiO2 /SWNT with different SWNT contents. The amount of PAni/HA/TiO2 /SWNT nanorods/tubes is signicantly decreased with increasing of SWNT content. Refer to the SEM images, smooth CNT ber is the CNT that not covered by PAni/HA layer and rough CNT ber is the CNT covered by PAni/HA layer. The thickness of PAni/HA layer is directly proportional to the polymerization time of PAni. The amount of smooth CNT bers (CNT that being circled in Fig. 5) is signicantly increased with increasing of CNT content. PAni/HA/TiO2 /SWNT with 60% of SWNT produces large amount of smooth CNT bers compared with those of 10% and 20% SWNT. In general, the key parameters that affect the conductivity of conjugated-polymers are interchain distance and localization length. All these parameters are clearly related to the way the

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polymers are synthesized [31]. Thus, it is really important to control the synthesis parameters, such as types of dopant or additives used in order to control the conduction properties of polymers. Electrical conductivities of PAni nanocomposites that consist of CNT (Table 1) are suitable (102 to 100 S/cm) to be used as better microwave absorber and shielding materials [9]. Compared with PAni/HA (1.88 104 S/cm), the conductivity of PAni/HA/TiO2 (1.62 106 S/cm) is significantly decreased after addition of TiO2 due to the partial blockage of conductive pathways by TiO2 that embedded in PAni matrix. However, the conductivity of PAni/HA/SWNT, PAni/HA/MWNT, PAni/HA/TiO2 /SWNT and PAni/HA/TiO2 /MWNT suddenly increase after addition of CNT. Besides that, the conductivity of PAni/HA/TiO2 /SWNT shows signicant improvement from 10%, followed by 20%

Fig. 2. Proposed mechanism for the formation of PAni/HA/TiO2 /CNT and PAni/HA/CNT: (a) formation of nanorods/tubes and (b) CNT enwrapped with PAni layers.

Fig. 1. (a) Proposed mechanism for the formation of PAni/HA/TiO2 , (b) SEM image of PAni/HA and (c) SEM image of PAni/HA/TiO2 .

and 60% of SWNT. PAni/HA/TiO2 /SWNT with 60% of SWNT exhibits the highest conductivity (7.15 100 S/cm) among the PAni nanocomposites. The temperature dependence of resistivity of PAni with CNT is lower than PAni itself and hence the delocalization of charge carriers is greater in PAni with CNT as reported by Feng et al. [23]. In general, charge carriers of CNT are always restricted to the boundary of CNT. However, charge carriers are also located between the interface of CNT and PAni other than the CNT boundary during in situ polymerization because the CNT is packed underneath the PAni (as shown by SEM images) compared with those prepared by ex situ polymerization. It is also proposed that CNT plays an important role to form a bridge to connect one PAni chain with another PAni chain to facilitate the movement of charge carriers among the intrachain of PAni. Hence, that is the reason of the improvement of conductivity of PAni nanocomposites after addition of CNT. Saturated magnetization (Ms ), remnant magnetization (Mr ) and coercive force (Hc ) were determined from the magnetization curves. Both PAni/HA/MWNT and PAni/HA/TiO2 /MWNT show higher magnetization (larger Ms ) compared with PAni/HA/SWNT and PAni/HA/TiO2 /SWNT due to the

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Fig. 3. SEM images of (a) PAni/HA/SWNT (30,000 magnication), (b) nanorods/tubes (60,000 magnication) and (c) CNT enwrapped with PAni layers (60,000 magnication).

Fig. 4. SEM images of (a) PAni/HA/TiO2 /SWNT (30,000 magnication), (b) nanorods/tubes (60,000 magnication) and (c) CNT enwrapped with PAni layers (60,000 magnication).

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Fig. 5. SEM images of PAni/HA/TiO2 /SWNT with different SWNT contents (a) 10%, (b) 20% and (c) 60%.

strong magnetization of MWNT. The magnetization of PAni/HA/TiO2 /SWNT is signicantly improved with increasing of SWNT inclusion from 10% to 60%, as the magnetic effect is gradually enhanced. The enhancement of magnetic effect will improve the interaction between PAni with CNT and thus creates additional magnetic inuence such as increasing of anisotropy or eddy current which may induce the microwave absorbing and shielding behavior of PAni [32]. Magnetic properties of PAni/HA/TiO2 /CNT are due to the proton irradiation that results in C H bond formation in CNT and give rise to the formation of large number of atomic vacancies and carbon interstitials which will inuence the magnetic properties of the resulted nanocomposites [33]. For microwave absorption study, toroidal sample with thickness of 2.5 mm was put into a 7.0-mm coaxial measurement cell of microwave vector network analyzer. The complex scattering parameters correspond to reection (S11*) of a transverse electromagnetic (TEM) wave were measured from 0.4 to 18 GHz. A full one-port calibration was carried out before measurement in order to reduce or remove errors due to the source match, load match, directivity and isolation during measurement. S11* was investigated based on a single-layered plane wave absorber backed by a perfect conductor. So, transmission of microwave during measurement is assumed as 0% [34]. The real and imaginary parts of complex dielectric permittivity ( = r jr ) of r the samples were also being investigated. The instrument was calibrated using air as standard, where r = 1, r = 0, r = 1 and r = 0. Reection losses (RL) of the samples (Fig. 6) were calculated by using the formula, RL = 20 log S11*. The microwave absorbance of the samples can be predicted from RL in which the larger the negative value of RL, the greater the microwave absorption properties of materials [35]. The dip in RL indicates the occurrences of absorption or minimal reection of microwave power. The intensity and frequency at RL minimum are depend on the properties and thickness of samples. The loss tangent (tan ) of samples can be calculated from the real and imaginary parts of complex dielectric permittivity by using the formula tan = r / r (Fig. 7). Materials with higher tan are considered as lossy materials that indicate strong absorption. Thus, the value of loss tangent could predict the microwave absorbance of the PAni [22]. In general, electronic, ionic, orientational and space charge polarizations are four factors mainly contribute to the dielectric behavior of a material. The space charge contribution depends on the inhomogeneity (or heterogeneity) of the material [36]. Dielectric response corresponds to intrinsic metallic nature of conductive polymer such as conductivity and charge delocalization that results in polarization of the material ( r ) and polarization of the structure of polymer [37]. The high values of dielectric constant are characteristics of conducting polymers which are partially attributed by the disordered motion of charge carriers along the backbone of polymer [5]. PAni nanocomposites with large amount of nanorods/tubes or CNT rough bers covered by PAni layers might possess higher heterogeneity that enhance the dielectric permittivity of materials. The improvement of dielectric property will enhance

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Fig. 6. Reection loss (RL) of (a) PAni/HA/CNT and PAni/HA/TiO2 /CNT and (b) PAni/HA/TiO2 /SWNT with different SWNT contents.

the microwave absorbing and shielding property of PAni. EMI shielding by absorption may be enhanced by increasing of skin depth, which is controlled by changing electrical conductivities, magnetic or dielectric constants of electrically conducting polymers [38]. As shown in Fig. 6(a), both PAni/HA/SWNT (RL = 14.2 dB, 94% absorption) and PAni/HA/MWNT (RL = 18.6 dB, 99% absorption) show higher absorption compared with PAni/HA/TiO2 /SWNT (RL = 9.0 dB, 80% absorption) and PAni/HA/TiO2 /MWNT (RL = 15.4 dB, 95% absorption) in frequency range of 515 GHz. This may

Fig. 7. Loss tangent of PAni/HA/TiO2 /SWNT with different SWNT contents.

be due to the higher conductivity of PAni/HA/SWNT and PAni/HA/MWNT that leading to more disordered motion of charge carriers along the backbone of PAni and thus improving the microwave absorbing property of PAni compared with PAni/HA/TiO2 /SWNT and PAni/HA/TiO2 /MWNT. PAni nanocomposites after addition of TiO2 seem like unavored for microwave absorption efciency since the results show poor conductivity and low magnetization compared with those samples without addition of TiO2 . The decrease in conductivity is due to the partial blockage of conductive pathways by TiO2 that embedded in the PAni and the decrease in magnetization is because of the existence of TiO2 as barriers that reduce the interaction between PAni nanoparticles with CNT and thus reduce the magnetic inuence of the nanocomposites. Besides that, both PAni/HA/MWNT and PAni/HA/TiO2 / MWNT exhibit better microwave absorption property (RL = 18.6 (15.4) dB, 9599% absorption) than PAni/HA/SWNT and PAni/HA/TiO2 /SWNT (RL = 14.2 (9) dB, 8094% absorption) due to the higher magnetization of MWNT compared with SWNT. Interaction between MWNT particles create additional magnetic inuence such as increasing of anisotropy or eddy current that result PAni/HA/MWNT and PAni/HA/TiO2 /MWNT exhibit promising microwave absorption property. Refer to Fig. 6(b), both PAni/HA and PAni/HA/TiO2 with poor conductivity and lower magnetization lead to less disordered motion of charge carriers along the backbone of polymer and hence reduce the microwave absorption behavior of PAni (RL < 6.1 dB, <60% absorption) compared with PAni/HA/TiO2 /SWNT with various contents of SWNT. Among PAni nanocomposites prepared in this study, PAni/HA/TiO2 /SWNT with 20% SWNT possesses the best microwave absorption property (99.2% absorption), parallel with the highest tan as shown in Fig. 7, in which the RL is 21.7 dB at 6 GHz. It is because PAni/HA/TiO2 /SWNT with 20% SWNT exhibits the promising combination of properties such as high conductivity, magnetization, largest tan and highest heterogeneity (large amount of nanorods/tubes and CNT covered by PAni layers) which might cause more disordered motion of charge carriers and exhibit greater molecular polarization phenomena, such as greater space charge relaxation, dipole rotation and hopping of conned charges [17]. Hence, it might induce current when incident EM waves penetrate the surface of PAni nanocomposite. Finally, the electrical energy dissipated by PAni could be signicantly enhanced and nally improve the microwave absorption of PAni [39]. In this report, the optimum content of SWNT for PAni/HA/TiO2 /SWNT is 20%. Addition of SWNT greater than 20% (such as 60%) results larger amount of smooth CNT ber without covered by PAni layer. Besides that, aggregation of CNT easily happens when SWNT content exceed the optimum value and might cause barrier inside the nanocomposites. Thus, the lower heterogeneity and aggregation formed will lead to demagnetizing effect and magnetic anisotropy that optimize the microwave permeability of PAni. Hence, this will signicantly affect the

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microwave absorption property of PAni/HA/TiO2 /SWNT with 60% SWNT (RL = 6.2 dB, 62% absorption) compared with those with 20% SWNT (RL = 21.7 dB, 99.2% absorption). Basically, the structure of microwave absorbing materials consists of shapes with properties that allow EM waves to penetrate into the regions where electric and magnetic elds experience loss. The loss is typically generated through the nite conductivity for dielectric absorber. When incident EM waves penetrate the surface of a conductive material, electric eld will interact with mobile electrons in the materials and thus induce current. Additional loss of absorber also happens through molecular polarization phenomena, such as space charge relaxation, dipole rotation and hopping of conned charges [17]. Then, electrical energy is dissipated as heat due to the resistance of materials [39]. The dissipative energy is said to have been absorbed by the material. In this report, PAni/HA/SWNT, PAni/HA/MWNT and PAni/HA/TiO2 /SWNT show RL < 15 dB (>95% absorption) from 4 to 8 GHz. Therefore, PAni/HA/TiO2 /CNT nanocomposites are suitable to be applied as microwave absorbing and shielding materials with moderate attenuation and broad bandwidth (4 GHz) at microwave frequencies. PAni/HA/TiO2 /SWNT with 60% SWNT exhibits RL < 20 dB (>99% absorption) with narrow bandwidth (1 GHz) at microwave frequencies. 4. Conclusion Novel PAni/HA/TiO2 /CNT nanomaterials with different synthesis parameters were successfully synthesized. Synthesis parameters such as addition of TiO2 , SWNT and MWNT, and different SWNT contents are signicant factors which will affect the magnetization, dielectric and conductivity of PAni and thus affect the microwave absorption property of PAni. PAni/HA/TiO2 /SWNT with 20% SWNT exhibits the most promising microwave absorption property (99.2% absorption). PAni/HA/TiO2 /CNT are suitable to be applied as microwave absorbing and shielding materials with moderate high attenuation (RL < 15 dB) and broad bandwidth at microwave frequencies. PAni/HA/TiO2 /SWNT with 60% SWNT exhibits RL < 20 dB with narrow bandwidth at microwave frequencies. Acknowledgements The author would like to show high appreciation for the Japan Government Scholarship (Monbukagakusho) for the nancial support. Microwave measurements were made at The Yokohama Rubber Co. Ltd., Japan. Besides that, author would like to thanks Professor Osamu Ishii and Mr. Masaki Nakamura for the measurement of magnetization.

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