Synthetic Metals 160 (2010) 23152318

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Enhanced microwave absorption properties in polyaniline and nano-ferrite composite in X-band

S.P. Gairola a , Vivek Verma a,b , Lalit Kumar b , M. Abdullah Dar a , S. Annapoorni b , R.K. Kotnala a,
a b

National Physical Laboratory (CSIR), Dr. K. S. Krishnan Road, New Delhi 110 012, India Department of Physics and Astrophysics, University of Delhi, Delhi 110007, India

a r t i c l e

i n f o

a b s t r a c t
Highly conducting polyaniline (PANI) nanocomposite with Mn0.2 Ni0.4 Zn0.4 Fe2 O4 ferrite was prepared by mechanical blending. The present work reports the EMI shielding characteristics of the ferrite-Pani nanocomposite with different thickness. The saturation magnetization (Ms) for pure MnNiZn ferrite (52 emu/g) and composite (41 emu/g) was measured by VSM at room temperature. The crystalline size of MnNiZn ferrite was found in the range of 2530 nm as analyzed by TEM and XRD. The complex permittivity, permeability and shielding effectiveness of the composite for different thicknesses were measured in the 812 GHz (X-band) frequency range. The composite of 2.5 mm thickness has shown high shielding effectiveness (49.2 dB) due to absorption (SEA ). The high value of SEA suggests that this composite can be used as a promising absorbing material for X-band frequency range. 2010 Elsevier B.V. All rights reserved.

Article history: Received 17 May 2010 Received in revised form 28 August 2010 Accepted 31 August 2010 Available online 28 September 2010 Keywords: Conducting polyaniline Ferrites Nanocomposite Shielding effectiveness

1. Introduction Polymer based composites with electroconductive properties have found use in numerous high technology applications in energy storage [1], electro-optical devices [2] and electromagnetic shielding [35]. With the increasing use of electronic products and telecommunication equipment, electromagnetic interference (EMI) has become a major problem, as it reduces the life time and efciency of the instruments. To reduce the impact of the EMI, EMI shielding materials have been widely investigated. Typically, metals have been used for EMI shielding materials as they have a high conductivity and dielectric permittivity [6,7]. However, metals have disadvantages, such as their weight, corrosion properties and poor processibility [8]. Electrically conductive polymer and ferrite composites can be used as EMI shielding materials to circumvent the disadvantages seen in metals [9,10]. Among several conducting polymers, polyaniline (PANI) is the most promising polymer for different potential applications, because of its excellent environment stability combined with relative high conductivity. Polyaniline can be dispersed into metallic llers like ferrites. This study is inspired by the recent advances in development of materials with magnetically controlled attenuation.

2. Experimental details 2.1. Synthesis of the Mn0.2 Ni0.4 Zn0.4 Fe2 O4 nano-particles The mixed ferrite with the composition Mn0.2 Ni0.4 Zn0.4 Fe2 O4 was prepared by citrate-gel precursor technique. All high purity chemicals Mn(NO3 )2 .4H2 O, Ni(NO3 )2 .6H2 O, Zn(NO3 )2 .6H2 O and Fe(NO3 )3 .9H2 O were used to synthesize the required compound. The homogeneous aqueous solutions of each metal nitrate salt were formed in distilled water separately. Then all these solutions were mixed in citric solution drop by drop with constant stirring. The homogeneous solution was slowly evaporated at 40 C to form a viscous gel. Subsequently gel was kept in furnace at 100 C to obtain the porous powder followed by self-combustion. 2.2. Synthesis of PANI Polyaniline in emeraldine state was prepared by chemical oxidation of aniline monomer [11]. Aniline monomers were dispersed in 1 M aqueous HCl (hydrochloric acid) and cooled down to below 5 C. Ammonium persulphate was used as an oxidant, was added drop wise to the above cooled solution of aniline monomers under rigorous stirring for 2 h. The solution was kept for 12 h to let the reaction complete. The polyaniline powder obtained was washed with distilled water and dried at 60 C. This was followed by reuxing in methanol for 12 h using a soxhlet assembly in order to remove the oligomers (small polymer chains) and dried at room temperature. The powder obtained by the above mentioned procedure is doped form of the polyaniline powder. The doped powder

Corresponding author. Tel.: +91 11 45608599. E-mail addresses: rkkotnala@mail.nplindia.ernet.in, vermavk@mail.nplindia.ernet.in (R.K. Kotnala). 0379-6779/$ see front matter 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.synthmet.2010.08.025

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Fig. 1. XRD diffraction pattern of Mn0.2 Ni0.4 Zn0.4 Fe2 O4 .

of the polyaniline was used to make the nanocomposites with Mn0.2 Ni0.4 Zn0.4 Fe2 O4 nano-ferrite particles. 2.3. Synthesis of composites The composite was prepared by blending of polyaniline powder with Mn0.2 Ni0.4 Zn0.4 Fe2 O4 nano-particles in 20:80 weight ratios. The rectangular samples of thickness 2, 2.5 and 3 mm were prepared to calculate shielding parameters. 2.4. Characterization The magnetic measurements of pure ferrite and composite were carried out using vibrating sample magnetometer (Lakeshore, 7304). Phase analysis of ferrite sample was investigated by Xray diffraction (XRD, Rigaku Miniex, Step size = 0.02) with CuK radiation of wavelength = 1.5406 A. FTIR spectra of samples was recorded in KBr medium in the wave number range 4004000 cm1 using a Perkin Elmer FTIR (Spectrum BX). The particle size of ferrite samples was observed from TEM (JEM 200CX). The rectangular samples (25 13 t mm) of different thickness t = 2, 2.5 and 3 mm of composite sample were inserted into a standard coaxial sample holder whereas reection coefcient S11 , transmittance coefcient S12, complex permittivity and complex permeability were measured by an Agilent E8362B Vector network analyzer (VNA) in frequency range of 812 GHz. The holder matches the internal dimensions of X-band (812 GHz) waveguide placed between the two ports of Vector Network Analyzer. 3. Results and discussion The XRD pattern of the as-prepared ferrite powder is shown in Fig. 1. The average crystalline size of ferrite powder estimated from the broadening of the diffraction peak (3 1 1), using Scherrers formula D = k / cos , where D is the average crystalline size, is the X-ray wavelength, is the full-width at half-maximum (FWHW) and is the diffraction angle. The value of k depends on several factors, including the miller index of reection plane and the shape of crystal. If shape is unknown, k is often assigned a value of 0.89. The average crystalline size of the ferrite particle was 25 nm determined by above formula, which is in accordance with TEM measurement. It is observed that the particle size of pure ferrite powder is in the range of 2530 nm. A slight agglomeration is also observed, which is due to the high surface energy and magnetic interactions of nano-particles.

Fig. 2. FTIR spectra of (a) pure PANI and (b) Mn0.2 Ni0.4 Zn0.4 Fe2 O4 sample.

Fig. 2 shows FTIR spectra of pure PANI and Mn0.2 Ni0.4 Zn0.4 Fe2 O4 nano-ferrite. In ferrite, metal ions are usually situated in two different sublattices designated as tetrahedral and octahedral sites. The characteristic peaks of PANI occur at 1555, 1470, 1298, 1239, 1134 and 508 cm1 as shown in Fig. 2(a). The peaks at 1555 and 1470 cm1 are attributed to the characteristic C C stretching of the quinoid and benzenoid rings, the peaks at 1298 and 1239 cm1 correspond to NH bending and asymmetric CH stretching modes of the benzenoid ring, respectively. The strong peak around 1134 cm1 is associated with vibration modes of N = Q = N (Q refers to the quinonic type rings), indicating that PANI polymer is formed in our sample [12]. It can be predicted from Fig. 2(b) that the peak 578 cm1 is intrinsic vibration for Mn0.2 Ni0.4 Zn0.4 Fe2 O4 sample. Fig. 3 shows the magnetization (M) versus the applied magnetic eld (H) for Mn0.2 Ni0.4 Zn0.4 Fe2 O4 and ferritePANI nanocomposite (8020 wt%) at room temperature. The saturation magnetization (Ms) for nano-Mn0.2 Ni0.4 Zn0.4 Fe2 O4 and ferritePANI composite is 52 emu/g and 41 emu/g, respectively. Saturation magnetization value reduces more than expected value due to the existence of non-magnetic medium PANI polymer in composite. This could be due to surface pinning of nano-ferrite particle spin in easy axis of the magnetization. Pinning of spin in easy axis of the magnetization leads to decrease in coercivity which has been in our samples as shown in Fig. 3. The EMI shielding effectiveness (SE) of a material is dened as the ratio of transmitted power to incident power and is given by SE (dB) = 10 log(Pt /P0 ), where Pt and P0 are the transmitted and incident electromagnetic powers respectively. For a shielding material, total SE = SER + SEA + SEM , where, SER is due to reection, SEA is due to absorption and SEM is due to multiple reections. In two port network, S parameter S11 (S22 ), S21 (S12 ) represents the reection

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Fig. 3. Magnetic hysteresis loops of pure Mn0.2 Ni0.4 Zn0.4 Fe2 O4 and ferritePANI composite.

Fig. 5. A linear response of SEA as function of ( with frequency (inset) for sample B.

1/2 ac )

and change in skin depth ()

convenient to express the reectance and effective absorbance in the form of 10 log(1 R) and 10 log(1 Aeff ) in decibel (dB), respectively, which results in SER and SEA as SER = 10 log(1 R) and SEA = 10 log(1 Aeff ) = 10 log[T/(1 R)]. Fig. 4 shows response of EMI shielding effectiveness, SEA and SER of ferritePANI nanocomposite having different thickness versus frequency in X-band. FerritePANI nanocomposite has shielding effectiveness (SE) mainly due to absorption which is found maximum 50 dB for sample B (2.5 mm thickness). The shielding effectiveness is found to decrease when thickness of the sample has been smaller or greater than 2.5 mm. The shielding effectiveness due to reection was nominal and values of SER lies between 1.8 and 3.3 dB. According to classical electromagnetic theory the EMI shielding effectiveness for far-eld shielding through the thick shield of thickness (d), conductivity ( ac ) and magnetic permeability ( ) can be expressed from following relation (1) [14]:
Fig. 4. Response of EMI shielding effectiveness, SEA and SER of ferritePANI nanocomposite having different thickness A (2 mm), B (2.5 mm) and C (3 mm), with frequency in X-band.

SE (dB) 10 log

ac

160

+ 20

log e

(1)

and the transmission coefcients T = |ET /EI |2 = |S21 |2 = |S12 |2 , and R = |ER /EI |2 = |S11 |2 = |S22 |2 and absorption coefcient (A) = 1 R T. Here, A is given with respect to the power of the incident EM wave. If the effect of multiple reections between both interfaces of the material is negligible, the relative intensity of the effectively incident EM wave inside the material after reection is treated equal to 1 R. Hence, 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 [13]. It is

where ac conductivity is related with the permittivity loss ac = 0 and the skin depth () is related with the ac conduc1/2 . The rst term tivity and magnetic permeability as = (2/ ac ) in above Eq. (1) is shielding effectiveness due to reection and second is due to the absorption of the electromagnetic wave. Therefore from Eq. (1) shielding effectiveness due to reection and due to absorption can be expressed by Eqs. (2) and (3), respectively. SER = 10 log
ac

16

r 0

(2)

Fig. 6. Response of real (a) and imaginary (b) part of permittivity of ferritePANI nanocomposite having different thickness A (2 mm), B (2.5 mm) and C (3 mm), with frequency in X-band.

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SEA = 20d

ac

1/2

log e

(3)

composite of 2.5 mm thickness has shown high shielding effectiveness (49.2 dB) due to absorption (SEA ). Acknowledgements The authors are grateful to Director, National Physical Laboratory; New Delhi for providing constant encouragement and motivation to carry out this work. The authors are grateful to Dr. S.K. Dhawan, NPL New Delhi to provide the facility of EM absorbing measurements. References
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Fig. 5 shows that SEA give a approximate linear response with respect to square root of ac conductivity where as variation in skin depth () with respect to frequency has been shown in the inset of gure. The complex permittivity and permeability of the ferritepolyaniline nanocomposite with different thickness were obtained from scattering parameters S11 and S21 using NicholsonRossWeir method [15,16]. The variation of real and imaginary part of permittivity with respect to frequency is shown in Fig. 6. The value of real part of permittivity is found to decrease with respect to frequency for all samples. The decrease in is due to lagging of dipole moment of polaron/bipolaron (PANI) with respect to external microwave frequency and magnetocrystalline anisotropy of nano-ferrite [13]. FerritePANI nanocomposite sample B (thickness 2.5 mm) exhibits highest permittivity ( ) value (40) which may be attributed to enhanced value of SE due to absorption. 4. Conclusions Conducting polymer PANI and nano-Mn0.2 Ni0.4 Zn0.4 Fe2 O4 ferrite composite was prepared by mechanical blending. The microwave absorption property strongly depends on intrinsic parameters ac conductively, permittivity of the nanocomposite of Mn0.2 Ni0.4 Zn0.4 Fe2 O4 ferrite and PANI. We have demonstrated that a high level of shielding performance can be achieved by the composite of PANI and nano-Mn0.2 Ni0.4 Zn0.4 Fe2 O4 ferrite. The