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Journal of Magnetism and Magnetic Materials 309 (2007) 2024 www.elsevier.com/locate/jmmm

Complex permittivity, complex permeability and microwave absorption properties of ferritepolymer composites
S.M. Abbasa,b,1, A.K. Dixitb, R. Chatterjeea,, T.C. Goelc
a

Department of Physics, IIT Delhi, Hauz Khas, New Delhi 110016, India b DMSRDE, G. T. Road, Kanpur 208013, India c BITS, PilaniGoa Campus, Zuari Nagar, Goa 403726, India Received 24 December 2005; received in revised form 30 May 2006 Available online 5 July 2006

Abstract The complex permittivity (e0 je00 ), complex permeability (m0 jm00 ) and microwave absorption properties of ferritepolymer composites prepared with different ferrite ratios of 50%, 60%, 70% and 80% in polyurethane (PU) matrix have been investigated in X-band (8.212.4 GHz) frequency range. The M-type hexaferrite composition BaCo+2Fe+2 Si+4 Fe+3 O19 was prepared by solid-state reaction 0.9 0.05 0.95 10.1 technique, whereas commercial PU was used to prepare the composites. At higher GHz frequencies, ferrites permeabilities are drastically reduced, however, the forced conversion of Fe+3 to Fe+2 ions that involves electron hopping, could have increased the dielectric losses in the chosen composition. We have measured complex permittivity and permeability using a vector network analyzer (HP/Agilent model PNA E8364B) and software module 85071. All the parameters e0 , e00 , m0 and m00 are found to increase with increased ferrite contents. Measured values of these parameters were used to determine the reection loss at various sample thicknesses, based on a model of a single-layered plane wave absorber backed by a perfect conductor. The composite with 80% ferrite content has shown a minimum reection loss of 24.5 dB (499% power absorption) at 12 GHz with the 20 dB bandwidth over the extended frequency range of 1113 GHz for an absorber thickness of 1.6 mm. The prepared composites can fruitfully be utilized for suppression of electromagnetic interference (EMI) and reduction of radar signatures (stealth technology). r 2006 Elsevier B.V. All rights reserved.
Keywords: Ferritepolymer composite; Hexaferrite; Complex permeability; Reection loss; Microwave absorption

1. Introduction The microwaves in higher GHz ranges are increasingly exploited by circuitry designers in the industries dealing with wireless telecommunication systems, radar, local area network, medical equipments, etc., due to saturation in lower frequency bands. This is, however, posing a serious problem of electromagnetic interference (EMI) and electromagnetic compatibility (EMC) in higher GHz range [1,2]. In order to provide solution to EMI/ EMC problem in higher GHz range, microwave absorbers in higher GHz range are in high demand [3,4]. An appropriate microwave
Corresponding author. Tel.:+91 11 2659 1354; fax: +91 11 2658 1114.

E-mail address: rmala@physics.iitd.ac.in (R. Chatterjee). Registered for Ph.D. degree in IIT Delhi, Hauz Khas, New Delhi 110016, India.
1

absorber in electronic equipments controls the excessive self-emission of electromagnetic waves and also ensures the undisturbed functioning of the equipment in presence of external electromagnetic wave. Microwave absorbers are also highly demanded in defence and aerospace industries, as the application of microwave-absorbing coating on the exterior surfaces of military aircraft and vehicles helps to avoid detection by the radar (Stealth technology) [5]. M-type hexaferrites are the most promising materials and extensively used for the development of microwave absorbers in higher GHz range because of their large tunable anisotropy eld (Ha 2 K/Ms) causing magnetic resonance in 252 GHz [6-12]. However, due to reduced magnetic permeabilities of ferrites in higher GHz range, resonance absorption is weak, and also in narrow frequency range. Alternatively, ferrites can be engineered to show enhanced dielectric losses in wide frequency

0304-8853/$ - see front matter r 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2006.06.006

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S.M. Abbas et al. / Journal of Magnetism and Magnetic Materials 309 (2007) 2024 21

range by appropriate choice of composition and heat treatment. In the chosen hexaferrite composition, BaCoxFe+2ySix+yFe+3 122x2yO19 (x 0.9 and y 0.05), Fe+3 ions are forced to convert into Fe+2 ions by the excess Si+4 (0.05) ion substitution. The electron hopping between Fe+3 and Fe+2 ions is expected to enhance the dielectric losses. In the present study, we have prepared ferritepolymer composites based on different ratios of the synthesized ferrite in polyurethane (PU) matrix and measured the complex permittivity and complex permeability in X-band frequencies (8.212.4 GHz). The reection losses in the composite samples were also determined at different X- band frequencies and sample thicknesses, using a computer simulation based on a model of a singlelayered plane wave absorber backed by a perfect conductor [13]. The matching frequencies for minimum reection and the corresponding matching thicknesses for the best sample (80% ferrite) are also presented. 2. Experimental work 2.1. Synthesis of ferrite and preparation of composite samples Ba-hexaferrite was synthesized by standard ceramic route. The raw materials used, were barium carbonate (99%, CDH, India), silicon dioxide (98%, CDH, India), cobalt oxide (98%, CDH, India) and ferric oxide (97%, CDH, India). The stoichiometric proportion of powders were weighed and wet mixed in acetone medium for 8 h using a ball mill. This powder mixture was thermally treated at 1290 1C for 4 h in air to convert it into ferrite phase. Heat-treated powder was nally ground and sieved to 400 mesh to get particles size o50 mm. The hexaferrite structure was checked by X-ray diffraction (XRD) technique. The XRD results revealed that the homogeneous phase of M-type Ba-hexaferrite was obtained. Ferritepolymer composites were prepared by thoroughly mixing the ferrite in different weight ratios, 50%, 60%, 70% and 80% in two-pack PU matrix consisting polyol-8 (Ciba-Geigy, Switzerland) and hexamethylene diisocynate (E-Merck, Germany) taken in equal proportion. Thick ferritePU paste was poured in a suitable mould and then cured at 70 1C. The prepared composite samples are designated as FPU1, FPU2, FPU3 and FPU4 for increasing ferrite content from 50% to 80%. 2.2. Microwave measurements The samples were shaped to t exactly into rectangular X-band wave-guide (WR90) for microwave measurements. The complex scattering parameters that correspond to the reection (S11 or S22) and transmission (S21 or S12) in the composite samples were measured using a vector network analyzer (HP/Agilent, PNA E8364B). Full twoport calibrations were initially done on the test setup in order to remove errors due to the directivity, source match,

load match, isolation, etc., in both the forward and reverse direction. The complex permittivity and permeability were then determined from the measured scattering parameters using Agilent software module 85071, based on the procedure given in HP product note [14]. 3. Results and discussion 3.1. Permittivity spectra Figs. 1 and 2 show the complex permittivity spectra, real (er0 ) and imaginary (er00 ) parts, respectively, for the

16

14

FPU4

12

10
FPU3

'

FPU2

6
FPU1

4 8 9 10 11 12 13 Frequency (GHz)

Fig. 1. Real part of permittivity spectra of composite samples FPU1, FPU2, FPU3 and FPU4.

1.2

FPU4

0.8 "

FPU3

0.4

FPU2

FPU1

0.0 8 9 10 11 12 13

Frequency (GHz)
Fig. 2. Imaginary part of permittivity spectra of composite samples FPU1, FPU2, FPU3 and FPU4.

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composite samples FPU1, FPU2, FPU3 and FPU4 in the frequency range of 8.212.4 GHz. The er0 spectra of all the samples show insignicant variation in the whole frequency range used in the present work. However, the er0 values have increased from $5.3 for FPU1 to $14.3 for FPU4 with increasing ferrite content from 50% to 80%. The er00 spectra for FPU3 and FPU4 also show insignicant variation with frequency, but in case of FPU1 and FPU2 some wavy behaviour is observed. There is a gradual increase in er00 values around 0.2 for FPU1 to $1.2 for FPU4 with increasing ferrite percentage. The M-type Ba-hexaferrite (BaFe12O19) is a wellstudied crystal [15]. It has a two-formula hexagonal unit cell that can be described as RSR*S*. The S and S* are called the spinel blocks that consist of two oxygen layers, separated by a block R containing the barium ion. R* and S* are obtained from blocks R and S, respectively, by rotation over 1801 around the c axis. The structure possesses three kinds of interstitials sites viz., tetrahedral, octahedral and trigonal bi-pyramid with coordination of four, six and ve O2 ions. All the 12 Fe+3 ions are distributed in these three interstitial sites in a specic manner. The positive ions Ba+2 and Fe+3 at their respective positions form the electric dipoles with the surrounding negative O2 ions, contributing to dielectric constant (er0 ) through dipolar polarization and by dipole relaxation to dielectric loss (er00 ). When the pair of Co+2 and Si+4 ions substitute some of the Fe+3 ions more dipoles are generated, thereby, increasing both the dielectric constant and loss. The excessive Si+4 (y 0.05) ions in the present composition force the conversion of Fe+3 ions into Fe+2 ions, further increasing the dielectric constant and loss. Since the present non-stoichiometric composition, BaCoxFe+2y Six+yFe+3 122x2yO 19 (x 0.9 and y 0.05) has variety of positive ions of different valences, having different coordination with O2 ions; dipoles of different strength are formed. These different dipoles have different relaxation time, giving rise to different relaxation frequencies. The electron hopping between Fe+3 and Fe+2 ions also contribute to the dielectric loss due to enhanced conduction mechanisms giving rise to another relaxation frequency [16,17]. In case of a ferritepolymer composite, the contribution to dielectric constant and dielectric loss also occur due to interfacial polarization and its relaxation as the semiconducting ferrite particles separated by insulating matrix molecules giving rise to heterogeneity. Different relaxation frequencies of various dipoles formed in the ferrite structure, hopping of electrons and the relaxation due to interfacial polarization all are responsible for oscillatory behaviour of absorption in the samples. However, as the ferrite content in the composite is increased high and smooth loss curves are obtained. This can be attributed to the overlapping of individual relaxation peaks of different diploes and dominance of relaxation due to interfacial polarization.

3.2. Permeability spectra Figs. 3 and 4 show the complex permeability spectra, real (mr0 ) and imaginary (mr00 ) parts, respectively, for all the composite samples. In general, both mr0 and mr00 values increase as the ferrite percentage is increased in the composite (barring FPU2). The mr0 spectra for all the samples show a decreasing trend with increasing frequency. The mr00 spectra, however, show small resonance peaks for FPU1 and FPU2 at lower side of X-band frequency, whereas no such peak is observed for FPU3 and FPU4 samples. Ba-hexaferrite (BaFe12O19) with its large anisotropic eld (Ha 1.36 MA/m) exhibits a ferrimagnetic resonance peak at 47.6 GHz.The resonance peak, however, can be shifted to any frequency region by appropriate pair

1.28

1.24

1.20 '

1.16
FPU4 FPU3

1.12

1.08

FPU1 FPU2

1.04 8 9 10 11 12 Frequency (GHz)

13

Fig. 3. Real part of permeability spectra of composite samples FPU1, FPU2, FPU3 and FPU4.

0.14
FPU4

0.12
FPU3

0.10 " 0.08

FPU2 FPU1

0.06

0.04 8 9 10 11 12 13 Frequency (GHz)

Fig. 4. Imaginary part of permeability spectra of composite samples FPU1, FPU2, FPU3 and FPU4.

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Reflection Loss (dB)

of divalent and tetravalent ions substitution in place of Fe+3 ions [18]. In the present ferrite composition, substitution by Co+2Si+4 (x 0.9) ions pair lowers the anisotropy eld, which has resulted the resonance peak at 8.5 GHz, which is evident from mr00 spectra of FPU1 and FPU2. The peak, probably, shifted beyond X-band towards lower side (not observed) with increased ferrite contents in FPU3 and FPU4. Kim et al. [19] had also observed the similar effect that is shifting of resonance peak towards low-frequency side with increased ferrite volume fraction for MnZn ferrite. The lower values of mr0 in case of FPU2 as compared to FPU1 are not understood. The oscillatory behaviour of mr00 can be understood on the basis of the precession motion of the magnetization vector. In a virgin hexaferrite, 12 Fe+3 ions are distributed in three different interstitial sites viz., tetrahedral, octahedral and one bi-pyramidal. The seven octahedral ions and one bipyramidal ion are oppositely coupled to two octahedral ions and two tetrahedral ions, giving a net magnetization of 4 Fe+3 pointing along the c axis. In this situation, magnetization vector on interaction with microwave precise in a stable manner yielding a smooth resonance curve. While, some of the Fe+3 ions are substituted by a pair of Co+2 and Si+4 magnetization vector shift towards basal plane. Bending towards basal plane is increased on higher substitution as in the present case. In this situation the magnetization vector precess in a zigzag manner, giving rise to oscillatory behaviour of absorption. Such behaviour is also observed by Meshram et al. [11]. However, at higher ferrite content, overlapping of precise motion of several crystallites results in a smoothened absorption curve. 3.3. Microwave absorbing properties Measured values of er0 , er00 , mr0 and mr00 as shown in Figs. 14 are used to determine the reection loss in the composite samples based on a model of a single-layered plane wave absorber proposed by Naito and Suetake [13]. In this model, the wave impedance (Z) at airabsorber interface is given as Z Zo(mr/er)1/2 tanh [(j2p/c) (mrer)1/2fd], where mr mr0 jmr00 and er er0 j er00 are the relative complex permeability and permittivity of the absorber medium, respectively. Zo 377 O and f are wave impedance and frequency, respectively, in free space, c is the velocity of light and d is the sample thickness. The reection loss (RL) in decibels (dB) is then determined as RL 20 log10 [j(ZZo)/(Z+Zo) j]. The impedancematching condition representing the perfectly absorbing properties is given by Z Zo. This condition is satised at a particular matching thickness (tm) and a matching frequency (fm), where minimum reection loss occurs. Fig. 5 shows the X-band absorption spectra for composites FPU1, FPU2, FPU3 and FPU4. The dip in reection loss is equivalent to the occurrence of minimum reection or maximum absorption of the microwave power for a particular sample thickness. The thicknesses of these

-5 Reflection Loss (dB)

t = 3.2mm

FPU1 FPU2

t = 2.6mm

FPU3 FPU4

-10

-15

t = 2.3mm

-20
t =1.85mm

-25 8 9 10 11 12 13 Frequency (GHz)

Fig. 5. Comparison of reection loss for FPU1, FPU2, FPU3 and FPU4 at centre frequency of X-band.

0
t=1.4mm

-5

t=1.6mm t=1.8mm

-10
t=2.0mm

-15
t=2.2mm

-20

-25 7 8 9 10 11 12 13 Frequency (GHz)

Fig. 6. Reection loss of the composite FPU4 (80% ferrite) at different sample thicknesses.

composites are optimized to bring the dip at the central frequency of X-band. FPU1 shows the minimum reection loss of 7 dB for sample thickness of 3.2 mm, FPU2 shows 12 dB at thickness of 2.6 mm, FPU3 shows 12.6 dB at thickness of 2.3 mm and FPU4 shows 21 dB at thickness of 1.85 mm. Fig. 6 shows, separately, the X-band absorption spectra for the composite FPU4 (80% ferrite) at different sample thicknesses: 1.4, 1.6, 1.8, 2 and 2.2 mm. This shows a minimum RL 24.5 dB at fm 12 GHz with the 20 dB bandwidth over the extended frequency range of 1113 GHz for tm 1.6 mm, a minimum RL 21.8 dB

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4. Conclusion
13

12

11

10

8 1.4 1.6 1.8 2.0 2.2

Matching thickness (mm)

Fig. 7. Relationship between matching frequency and matching thickness for composite FPU4 (80% ferrite).

The ferritepolymer composites with different ferrite ratios have been successfully prepared in PU matrix. The complex permittivity, permeability and their relationship with microwave absorption properties were investigated. It is found that the absorption properties in the composites are greatly improved with increasing ferrite contents in the polymer matrix. The composite with 80% ferrite content has shown a minimum reection loss of 24.5 dB at 12 GHz with a 20 dB bandwidth over the extended frequency range of 1113 GHz in a quite thin sample with a thickness of only 1.6 mm. A relationship between a matching thickness and a matching frequency has been established. It is found that the matching frequency for minimum reection decreases with increasing thickness of the composite. The prepared composites have potential applications in EMI shielding and reduction of radar signatures (Stealth technology). Acknowledgements The authors are grateful to the Director DMSRDE, Kanpur for extending the facility for microwave measurement. Reference
[1] A.N. Yusoff, M.H. Abdullah, J. Magn. Magn. Mater. 269 (2004) 271. [2] C.H. Peng, C.C. Hwang, J. Wan, J.S. Tsai, S.Y. Chem, Mater. Sci. Eng. B 117 (2005) 27. [3] S. Devender, R. Ramasamy, IEEE Conf. Proc. INCEMIC 97 (1997) 459. [4] D.D.L. Chung, Carbon 39 (2001) 279. [5] R.A. Stonier, SAMPE J. 27 (4) (1991) 9. [6] M. Pardavi-Horvath, J. Magn. Magn. Mater. 215216 (2000) 171. [7] S.M. Abbas, R. Aiyar, O. Prakash, Bull. Mater. Sci. 21 (1998) 279. [8] P. Singh, V.K. Babbar, A. Razdan, S.L. Srivastava, T.C. Goel, Mater. Sci. Eng. B 78 (2000) 70. [9] S. Sugimoto, S. Kondo, K. Okayama, H. Nakamura, D. Book, T. Kagotani, H. Ota, M. Kimura, R. Sato, IEEE Trans. Magn. 35 (1999) 3154. [10] H.S. Cho, S.S. Kim, IEEE Trans. Magn. 35 (1999) 3151. [11] M.R. Meshram, N.K. Agarwal, B. Sinha, P.S. Misra, J. Magn. Magn. Mater. 271 (2004) 207. [12] A. Verma, R.G. Mendiratta, T.C. Goel, D.C. Dube, J. Electroceram. 8 (2002) 203. [13] Y. Naito, K. Suetake, IEEE Trans. Microwave Theory Tech. 19 (1971) 65. [14] Hewlett-Packard Microwave Network Analyser Catalogue 8510 and Product Note 8510-3, 1987. [15] J. Smit, H.P.J. Wijn, Ferrites, Philips Technical Library, Eidehoven, Netherlands, 1959, pp. 240241. [16] S. Chikazumi, S.H. Charap, Physics of Magnetism, Wiley, New York, 1964 327pp. [17] Z. Haijun, L. Zhichao, Y. Xi, Z. Liangying, W. Mingzhong, Mater. Sci. Eng. B 97 (2003) 160. [18] H. Severin, J.P. Stoll, Z. Angew. Phys. 23 (1967) 209. [19] D.Y. Kim, Y.C. Chung, T.W. Kang, H.C. Kim, IEEE Trans. Magn. 12 (1996) 555. [20] A.N. Yusoff, M.H. Abdulla, S.H. Ahmad, S.F. Jusoh, A.A. Mansor, S.A.A. Hamid, J. Appl. Phys. 92 (2002) 876.

at fm 10.5 GHz with a 20 dB bandwidth over the frequency range of 9.911 GHz for tm 1.8 mm and 19 dB between 9.1 and 9.5 GHz for tm 2.0 mm. The minimum RL or matching condition is shifted beyond X-band for 2.0 mm otmo1.6 mm. It can be noticed in Fig. 5 that by increasing the ferrite content in the composite, the absorption in the sample can be increased and it also reduces the sample thickness. In Fig. 6 it can, further, be noticed that the dip showing minimum RL shifts towards a higher frequency side if the sample thickness is reduced. Contrary to the normal behaviour, however, absorption is increasing as the thickness is decreased. This can be understood based on quarter-wave principle [20]. When an electromagnetic wave is incident on an absorber sample backed by a metal plate, it is partially reected from air to absorber interface and partially reected from absorber to metal interface. These two reected waves are out-of-phase by 1801 and cancel each other at airabsorber interface for absorbers satisfying the quarter-wave thickness criteria: t lo/4 (jmrjjerj)1/2, where lo c/f is the free-space wavelength of incident wave and jmrj and jerj are the moduli of mr and er. As explained earlier, increased ferrite content in the composite increases the values of jmrjjerj, hence the thickness is reduced. Since, the thickness is inversely proportional to frequency, the above criterion is satised at reduced sample thickness for higher frequencies. The higher absorption at reduced thickness is the result of total cancellation, satisfying the above criteria perfectly. In case of absorber thicknesses not satisfying the criteria, only partial cancellation occurs, giving lower absorption. The matching thickness and matching frequencies for minimum reection are identied in case of FPU4 (80% ferrite) and their relationship is shown in Fig. 7. The matching frequency decreases almost linearly with the increase of absorber thickness.

Matching frequency (GHz)