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Materials Chemistry and Physics 113 (2009) 919–926

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Materials Chemistry and Physics
journal homepage: www.elsevier.com/locate/matchemphys

Polyaniline–MWCNT nanocomposites for microwave absorption
and EMI shielding
Parveen Saini a , Veena Choudhary b , B.P. Singh c , R.B. Mathur c , S.K. Dhawan a,∗
a

Polymeric & Soft Materials Section, National Physical Laboratory, New Delhi 110012, India
Centre for Polymer Science & Engineering, Indian Institute of Technology, New Delhi 110016, India
c
Carbon Technology Unit, National Physical Laboratory, New Delhi 110012, India
b

a r t i c l e

i n f o

Article history:
Received 15 July 2008
Received in revised form 12 August 2008
Accepted 14 August 2008
Keywords:
Composite materials
Fourier transform infrared spectroscopy
(FTIR)
Thermogravimetric analysis (TGA)
Electrical conductivity

a b s t r a c t
Highly conducting polyaniline (PANI)–multi-walled carbon nanotube (MWCNT) nanocomposites were
prepared by in situ polymerization. The FTIR and XRD show systematic shifting of the characteristic
bands and peaks of PANI, with the increase in MWCNT phase, suggesting significant interaction between
the phases. The SEM and TEM pictures show thick and uniform coating of PANI over surface of individual
MWCNT. Based on observed morphological features in SEM, the probable formation mechanism of these
composites has been proposed. The electrical conductivity of PANI–MWCNT composite (19.7 S cm−1 ) was
even better than MWCNT (19.1 S cm−1 ) or PANI (2.0 S cm−1 ). This can be ascribed to the synergistic effect
of two complementing phases (i.e. PANI and MWCNT). The absorption dominated total shielding effectiveness (SE) of −27.5 to −39.2 dB of these composites indicates the usefulness of these materials for
microwave shielding in the Ku-band (12.4–18.0 GHz). These PANI coated MWCNTs with large aspect ratio
are also proposed as hybrid conductive fillers in various thermoplastic matrices, for making structurally
strong microwave shields.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
The proliferation of electronics and instrumentation in commercial, industrial, healthcare and defense sectors has led to a
novel kind of pollution known as electromagnetic interference [1].
This is a serious issue caused by the interference effects of current
induced by electric and magnetic fields, emanating from nearby
wide range of electrical circuitry [2]. The interference among business machines, process equipments, consumer products and other
instruments may lead to disturbance of usual performance or even
complete malfunction. The disturbances across communication
channels, automation and process control may lead to loss of valuable time, energy, resources, money or even precious human life.
Therefore some kind of shielding mechanism must be provided to
guard the concerned article from spurious electromagnetic noises
or pollution. Metals are most common materials for EMI shielding
[3,4]. But they suffered from the disadvantages like high density,
susceptibility to corrosion, complex and uneconomic processing.
Further, metals mainly reflect the radiation and cannot be used

∗ Corresponding author. Tel.: +91 11 45609401; fax: +91 11 25726938.
E-mail address: skdhawan@mail.nplindia.ernet.in (S.K. Dhawan).
0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.08.065

in applications where absorption is prime requisite, e.g. in stealth
technology [5,6].
In the last four decades, conducting polymers (CPs) have gained
a special status owing to wealth of applications [7–15]. The EMI
shielding and microwave absorption properties of these polymers can be explained in terms of electrical conductivity and
presence of bound/localized charges (polarons/bipolarons) leading to strong polarization and relaxation effects [16,17]. Polyaniline
(PANI) has special status among other conducting polymers due
to its non-redox doping, good environmental stability and economic feasibility. The properties can be further tuned by controlled
polymerization conditions and using substituted anilines, specific
comonomers, dopants and fillers [18–22]. PANI has low inherent
specific strength and requires dispersion in some binding matrix
to form composites for any commercially useful product. However,
percolation threshold tends to be high due to low compatibilities,
phase segregated morphology and low aspect ratio of the conducting polymer particles. Therefore, high concentration of conducting
polymers is required in matrix for acceptable electrical properties
which often affect the mechanical properties of resultant composites.
Since their discovery [23], the exceptional mechanical, electrical and thermal properties of carbon nanotube (CNT) [24,25]
made them potential candidate for high-tech applications [26–30].

India) were used as received. we have proposed the probable formation mechanism of the PANI–MWCNT composites depicted schematically in Fig. 42 mm) that was kept at a constant temperature of 750 ◦ C. The thermal stability was measured under inert atmosphere of nitrogen using thermogravimetric analyzer (Mettler Toledo TGA/SDTA 851e ). Recently. UK) and TEM (Phillips. In the present experimental setup a single zone electric furnace has been used in the place of conventional two zone furnace. Materials Aniline (Loba Chemie. in the solution phase polymerization proceeds in uncatalyzed fashion and highly agglomerated polymer was formed which can be seen in the SEM. (NH4 )2 S2 O8 in 100 ml distilled water). These PANI coated MWCNTs may act as hybrid conductive filler for making composites with insulating matrices. 3.2. a slight shift was observed in the position of the main characteristic bands of doped PANI. Morphologies were observed using SEM (Leo 440.e. i. polymerization proceeds at much faster rate on the surface of MWCNTs than in solution phase. The 1120 cm−1 band of PANI becomes broader and shifted to 1106 cm−1 in PCNT25. The nanoporous coating of PANI may also acts as functional handle providing good dispersibility and processability of MWCNTs due to better interaction with host matrix.4–18. The MWCNT being electron acceptor and aniline being electron donor form a kind of weak charge transfer complex [46]. In this paper. However. Preparation of MWCNT MWCNTs have been synthesized by thermal decomposition of toluene in presence of iron catalyst obtained from organometallic ferrocene. sensors. The EMI shielding measurements were taken on pressed rectangular pellets (2 mm thick) placed inside the homemade sample holder. The material is heated from 25 to 700 ◦ C at a constant heating rate of 10 ◦ C min−1 . we report the potential of PANI coated MWCNT as possible microwave absorber. The dried mass was crushed to obtain the powder of the doped PANI (emeraldine salt) designated as PCNT0. As the polymerization of aniline takes place on the surface of MWCNTs.d. pellets of length 13 mm. poor dispersion and lack of interfacial adhesion of CNTs possess serious obstacles to their further development. The holder matches the internal dimensions of Ku-band (12. 25% for PCNT-5.35]. The 1290 and 1240 cm−1 bands are assigned to the bending vibrations of N–H and asymmetric C–N stretching modes of polaron structure of PANI. 5.920 P. several attempts have been made to introduce CNTs into the matrices of CPs. Therefore. / Materials Chemistry and Physics 113 (2009) 919–926 However. The purity of these tubes as determined from TGA was 88%. effective rate of deposition of PANI on MWCNTs is much faster than bulk polymerization in solution phase. The formation of complex is facilitated by the lone pair of electrons on the amine nitrogen of aniline monomer. 1.49. MWCNTs also act as polymerization catalyst. Merck. 20 and. The weight loss was continuously monitored as a function of temperature (or time). After complete polymerization the polymer was isolated from the dark green precipitate by filtration. at certain critical amount of MWCNT the polymerization exclusively takes place on the surface leading to uniform coating of PANI over MWCNT (see SEM and TEM). In a typical reaction. Saini et al. Like most other large surface area nanophase materials. The details of the experimental set up are given elsewhere [43]. the additional anilinium radical cations are constantly attached to the surface of MWCNT from the reaction medium.1 degree min−1 using D8 Advance Bruker AXS X-ray diffractometer. Therefore. India) was freshly distilled before use.1. The increase in the relative intensity of bands around 1480 and 1240 cm−1 may be attributed to the PANI attached to MWCNT [48]. This increases the generation of cation radicals on the surface of MWCNT which brings about the surface polymerization.42].1. The wet cake so obtained was dried under dynamic vacuum and crushed to form the powder. PCNT-20 and PCNT-25. The prominent absorption band around 1120 cm−1 (C–N stretching) is due to the charge delocalization over the polymeric backbone [44].1. The polymerization was initiated by drop wise addition of ammonium persulfate and allowed to propagate for 6 h. Therefore.1 mol of aniline was dissolved in aqueous solution of 1. The temperature of the mixture was maintained at 0 ± 0. The required weight of MWCNT was calculated from the desired percentage of MWCNT relative to aniline monomer. which indicates interaction of MWCNT with PANI matrix. The band around 798 cm−1 is due to the out of the plane C–H bending vibrations. optoelectronic devices [34. Mechanism of composite formation On the basis of basic concepts of polymerization and catalysis [45] and well supported by SEM/TEM measurements of our samples. CM-12). Experimental details 2. i. India) and ammonium presulfate (APS. Merck. With increase in MWCNT phase.0 M HCl. [36. through direct route using HCl as dopant [44]. The infrared spectra of powdered samples were taken at resolution of 4. .1. HCl acts as dopant and it also complexes with aniline facilitating its solubilization and dispersion. PANI–CNT composites have been proposed for EMI shielding applications [40] but only few brief reports are available on their microwave absorption characteristics [41.1 mol. The reaction mixture was filtered and washed repeatedly with distilled water until filtrate becomes colorless. These nanocomposites have shown promising response for futuristic applications like battery materials [33]. MWCNTs were synthesized in laboratory by chemical vapor deposition (CVD) route.1.0 cm−1 in 4000–400 cm−1 range. The polymer has been produced directly in the doped state as fine slurry of dark green particles. The XRD spectra of powdered samples were taken in 10–70◦ range at a scan rate of 0. On addition of oxidant. actuators [38] and electrorheology [39].5 mm were prepared using hydraulic press under pressure of 100 kg cm−2 . The control MWCNT sample was also prepared and designated as PCNT100. the reaction system is heterogeneous with presence of adequate aniline on the surface of MWCNT and the remaining aniline monomer in the solution phase. respectively.e. MWCNT. These are due to the conducting state of the polymer. This can be ascribed to the charge transfer interactions between the ␲conjugated surfaces of MWCNT and quinoid moiety of PANI–HCl [45. The bands near 1560 and 1480 cm−1 are characteristic stretching bands of nitrogen quinoid (N Q N) and benzenoid (N–B–N).2. Aqueous solutions were prepared from the double distilled water having specific resistivity of 106 Ohm-cm.1 ◦ C throughout the course of reaction (6 h). width 7 mm. This mixture was injected into a quartz reactor (o. 2 shows the FTIR spectra of PANI and PANI–MWCNT nanocomposites. 2. Measurements For the conductivity measurements. Synthesis of composites The composites were prepared in similar fashion by keeping the amounts of both HCl and aniline same as in preparation of pure PANI (PCNT0) and taking the additional component. 0. Synthesis of PANI The doped PANI was prepared by free radical chemical oxidative polymerization.3. Therefore. 2. 10. thickness 1. polymerization proceeds both in solution (bulk polymerization) and on the surface of MWCNTs. using NICOLET 5700 FTIR spectrophotometer and diamond ATR accessory. 2. FTIR spectra Fig. The above mixture was stirred continuously and the polymerization was initiated by the drop wise addition of ammonium persulfate (0. functionalization routes have been developed [31] that often manifested themselves in some deterioration of inherent properties of pristine CNTs [32]. To solve the above problems. The wet polymer cake so obtained was dried at 60 ◦ C under dynamic vacuum.50]. 2. The silver contacts were applied and the current–voltage (I–V) measurements were taken in four-probe configuration using Keithley 220 Programmable Current Source and 181 Nanovoltmeter. Hydrochloric acid (HCl. 2. respectively [47]. PCNT-10. Results and discussion 3.0 GHz) waveguide placed between the two ports of Vector Network Analyzer (VNA E8263BAgilent Technologies). 3.1.37].2. To combine the good properties of nanotubes and CPs. As the proportion of MWCNT increases the surface polymerization becomes more important than bulk polymerization.

Saini et al. 3 shows the XRD patterns of pure MWCNT. XRD studies Fig. (0 2 0). 1. 20. The characteristic peaks of the doped PANI (PCNT0) are observed around 2 values of 15. PANI and PANI–MWCNT nanocomposites. The pure MWCNT (PCNT100) shows a sharp peak centered on 2 value of 26◦ which corresponds to the (0 0 2) planes of MWCNT.3. Proposed mechanism for the formation of PANI–MWCNT nanocomposites. 25.P. The composites show the characteristic peaks of both PANI and MWCNT . 30◦ corresponding to (0 1 1). / Materials Chemistry and Physics 113 (2009) 919–926 921 Fig. (2 0 0) and (0 2 2) reflections of emeraldine salt form [52]. The peaks around 43◦ are due to the (1 1 0) and (1 0 0) graphitic planes plus small amount of catalyst particle encapsulated inside the walls of the MWCNTs [51]. 3.

5f) which even after pelletization represents poorly packed system [41]. XRD scans of PANI. control MWCNT (PCNT100. Variation of room temperature electrical conductivity of PANI–MWCNT nanocomposites with different loading levels of MWCNT. PANI and MWCNT) leads to conductivity of 19. Electrical conductivity The room temperature current–voltage (I–V) characteristics were measured and resistance values were obtained from the slope of these plots. Therefore. L RA (1) where “L” is the length of the pellet. The uniform coating of PANI reduces the disorder/voids in composites and improves intertubular charge transport leading to enhanced electrical properties. 4) was found to exhibit continuous increase with the increase in the MWCNT content. / Materials Chemistry and Physics 113 (2009) 919–926 Fig. which is even better than bulk conductivity of either phase alone. This increases the coherence or coupling between the chains and leads to enhancement of interchain transport. i. 2. The slight shifting in the peak positions may be ascribed to charge transfer interactions between PANI and MWCNTs leading to variations in chain packing and configurations.922 P. Further. without any additional bands indicating absence of covalent interactions between the phases [42]. 3.e. the reduced intertubular charge transport was responsible for observed low bulk conductivities. Fig. 4. This may be explained on the basis of cushioning effect of softer polyaniline coating over tubes which deforms easily during the pellet formation improving the surface contacts of coated tubes. “R” is resistance and “A” is crosssectional area of the pellets normal to direction of current flow.4. Saini et al. 19. 5 SEM images). As the MWCNT content increases. The conductivity (Fig. This synergistic effect of two complementing phases (i.e. The lower conductivity of bulk MWCNT pellet may be due to the fact that pressed pellets of uncoated MWCNTs contain highly entangled tubes (SEM Fig. the nanotubes can act as interconnecting bridge between the various conducting grains of the polyaniline. the relative intensity of characteristic bands of PANI decreases whereas bands of MWCNT become more prominent.1 S cm−1 ) or pure PANI (PCNT0. which are coated over individual MWCNTs. FTIR spectra of PANI–MWCNT nanocomposites with different nanotube content. The high conductivities of these composites are due to micrometer long MWCNTs as core and PANI coating as shell (see Fig. . Measurement of electrical conductivity of terphenyl and quaterphenyl films revealed that organic nanocrystallites play interface nano trapping levels effectively interacting with phonon subsystems [53]. Due to their highly conducting nature as well as high aspect ratio. MWCNT and PANI–MWCNT nanocomposites.0 S cm−1 ). Introduction of MWCNT to PANI enhances the electrical properties by facilitating the charge transfer processes between the two components [54].7 S cm−1 in case of PCNT25. These states may be principal for the achievement of conductivities varying in the large range of parameters. The electrical conductivities of the pellets can be calculated by considering the sample dimensions as: = Fig. the PANI–HCl coating is likely to facilitate the intertube charge transport by reducing the interfacial contact and tunneling resistances. 3. 2.

/ Materials Chemistry and Physics 113 (2009) 919–926 923 Fig. Inset shows TEM of PCNT25. (c) PCNT10. Therefore. 5a) exits as highly agglomerated globular particles whereas as grown MWCNTs (PCNT100) are entangled tubules (Fig. (b) PCNT5. PANI and PANI–MWCNT nanocomposites. (e) PCNT25 and (f) PCNT100. Thermogravimetric analysis (TGA) Fig. with the increase in MWCNT content. 5e) shows the presence of thick and uniform coating of PANI over surface of MWCNT. Morphological details Fig. 5 shows the SEM images of MWCNT. These TG plots show that weight loss occurs in several systematic steps each corresponds to the loss . SEM images of (a) PCNT0. 5f) with diameter in the range of 10–60 nm and their lengths ranging in several microns.6. PANI coated tubes exist as globular agglomerates (Fig. PANI and PANI–MWCNT nanocomposites. At very low concentration of MWCNTs. Saini et al. The SEM of PCNT25 also revealed the nanoporous nature of coatings. 5e). TEM of pure MWCNT [43] clearly shows that tubes are multiwalled with outer diameter in the range of 10–60 nm and their lengths ranging in several microns. The small size of the nanotubes having high specific surface area provides large number of sorption sites to aniline monomer which can polymerize to form coating over the nanotubes. These micrographs show that PCNT0 (Fig.5. 5. However. 3.P. 3. 6 shows the thermograms (TG) of the pure MWCNT. This may be attributed to the large proportion of bulk/solution polymerized PANI (existing in agglomerated form) as compared to aniline polymerized over MWCNT surface. 5b). 5b) towards uniformly coated tubules (Fig. which can be used for selective incorporation of other nanoparticles. at certain critical concentration of MWCNT (in our case achieved in PCNT25) the polymerization takes place exclusively on surface of MWCNT with minimal bulk polymerization and agglomeration effects. The TEM of the PCNT25 (inset Fig. there is systematic change in morphology from highly aggregated globules (Fig. (d) PCNT20.

Thermogravimetric (TG) traces of PANI.0 GHz). negative or zero. The evolved HCl acts as catalyst for the degradation reaction and rate of degradation increases with increase in the PANI proportion in the composites. the increasing amount of MWCNTs does not have much influence on the decomposition temperature of composites.924 P. respectively. In composites. The final loss step (470–700 ◦ C) corresponds to the complete breakdown of the polymeric backbone as well as heavier fragments into still smaller fractions and gaseous byproducts. The transmittance (T). iron catalyst residues and the carbonized polymeric fragments. cross linking of chains and onset of degradation of polymeric backbone. 7a.5%. there is always some overlap in weight loss ranges with no sharp transition between different steps. the total EMI SET obtained from Eq. 6. and absorbance (A) through the shielding material can be described as below:  2  ET   = |S12 |2 (= |S12 |2 ) E T =  2  ER   = |S11 |2 (= |S22 |2 ) E R= (7) I (8) I A=1−R−T (9) The SEM is a correction term whose value may be positive. The char residues (remaining at 700 ◦ C) are mainly thermally stable inert materials like MWCNTs. (a) Schematic of the VNA used for the measurement of shielding effectiveness in Ku-band (12. n is the refractive index of shielding material and Im(k) is the imaginary part of wave vector in the shielding material. / Materials Chemistry and Physics 113 (2009) 919–926 3. and multiple reflections (SEM ) as the following [59. EMI SE can be expressed as [55–58]: EMI SET = 10 log Fig.7. Fig. The fourth loss step (300–470 ◦ C) can be ascribed to the degradation of polymeric backbone into heavier fragments. The effect of multiple reflections between both interfaces of the material is negligible when SEA ≥ 10 dB [61]. absorption and multiple internal reflection losses at the existing interfaces. . (b) interaction of electromagnetic waves with shield material. absorption (SEA ). The S11 (or S22) and S12 (or S21) are the scattering parameters (S-parameters) of the two-port vector network analyzer (VNA) system and are shown schematically in Fig. For a single layer of shielding material. Saini et al. However. The pure nanotubes (MWCNT) have excellent thermal stability up to 700 ◦ C and weight loss was only 0. (2) is described as the sum of the contribution due to reflection (SER ). reflectance (R). of particular species. 7b.4–18. As evident from the TG traces. The second loss step (110–185 ◦ C) involves the loss of dopant in the form of HCl gas. the first step loss (25–110 ◦ C) may be attributed to the loss of sorbed water molecules. 7. the shielding is a direct consequence of reflection. As shown in Fig. MWCNT and PANI–MWCNT nanocomposites. As the amount of MWCNT increases. The third loss step (185–300◦ C) involves the loss of low molecular weight fragments. the corresponding char residue also increases indicating increased incorporation of nanotubes inside the PANI matrix.60]: SET = SER + SEA + SEM (dB)    (1 + n2 )    (dB) SER = 20 log  4n  SEA = 20 Im(k)d log e (dB)    1 − (1 − n2 )   (dB) SEM = 20 log  exp(2ikd)  (1 + n)2 (3) (4) (5) (6) Here. respectively. Shielding effectiveness (SE) EMI shielding is defined as the attenuation of the propagating electromagnetic waves produced by the shielding material. They represent the reflection and transmission coefficients.     PI  EI   HI  = 20 log   = 20 log   (dB) PT ET HT (2) where PI (EI ) and PT (ET ) are the power (electric field) of incident and transmitted EM waves. suffered by incident electromagnetic (EM) waves.

0 to −12. Materials with tan ı > 1 are considered as lossy materials having strong absorption characteristics. (14). The increase in the CNT content Fig. the earlier relations are no longer valid and further analysis of the S-parameters is required. It is convenient that reflectance and effective absorbance are expressed as the form of 10 log(1 − R) and 10 log(1 − Aeff ) in decibel (dB). Fig. respectively and “f” is the frequency of radiation. the relative intensity of the effectively incident EM wave inside the materials after reflection is based on (1 − R). The attenuation of wave by absorption is related to skin depth and thickness of the shield by [1]: SEA (dB) = K t ı = Kt(f) 1/2 (14) where “K” is a constant. lower plots) exhibits rapid enhancement from −18.0 GHz range) on the pressed rectangular pellets (2 mm thick) to suit the internal dimensions of Ku-band waveguides. respectively which provide the SER and SEA as follows: SER = 10 log(1 − R) dB  T SEA = 10 log(1 − Aeff ) = 10 log (1 − R) (10)  dB (11) In the case of non-negligible SEM . (12). Further. For nonmagnetic material. Loss tangent (tan ı = ε /ε ) is a good measure of the microwave absorption [41]. 9.4–18. leading to enhanced ohmic losses [42] in the proposed electromagnetic shielding material. “t” is thickness of the shield and “f” is the frequency of radiation.e. 9b) shows linear dependence confirming the validity of Eq. The increased conductivity may manifest itself as increase in both long range charge transport as well as number of possible relaxation modes. For a plane wave radiation the far field reflection loss can be expressed as [61]: SER (dB) = 108 + log  f (12) where “” and “” are conductivity and permeability of the medium. Shielding effectiveness of PANI and PANI–MWCNT nanocomposites in Kuband (12. Saini et al.0 GHz). 8 (upper plots) shows that reflection loss increases slightly from −8. 8. (13) reveals that increasing conductivity leads to corresponding decrease in skin depth which may be helpful in designing thinner EMI shields.4–18. Fig.5 to −28. Variation of loss tangent with increase in loading level of MWCNT.0 dB with the increase in MWCNT content which may be ascribed to increase in the conductivity of composites.  = 1). The absorption loss (Fig. can be expressed as [1]: ı = (f) −1/2 (13) where “ı” is skin depth and other symbols have usual meanings as defined above.P. . the effective absorbance (Aeff ) can be described as Aeff = (1 − R − T)/(1 − R) with respect to the power of the effectively incident EM wave inside the shielding material. The plot of SER (dB) versus ()1/2 (Fig. The plots of SER (dB) versus log  (Fig. the skin depth which can be described as the distance “ı” over which the amplitude of a traveling plane wave decreases by a factor e−1 . Eq. The average value of shielding effectiveness (SE) of the composites has been measured in the Ku-band (12. 10. 9a) are straight lines revealing the applicability of Eq. Therefore. Plots of (a) |SER | versus log() and (b) |SEA | versus ()1/2 . / Materials Chemistry and Physics 113 (2009) 919–926 925 Fig. 8.0 dB with the increased CNT loading. permeability can be taken as unity (i. Therefore. This may be explained in terms of increase in conductivity as well as capacitive coupling effects.

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