Electric and Dielectric Properties of Cr-Ga Substituted BaM Hexaferrites for HighFrequency Applications Ihsan Ali, M.U.Islam, M.S.

Awan & Mukhtar Ahmad

Journal of Materials Engineering and Performance ISSN 1059-9495 J. of Materi Eng and Perform DOI 10.1007/s11665-013-0562-7

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Electric and Dielectric Properties of Cr-Ga Substituted BaM Hexaferrites for High-Frequency Applications
Ihsan Ali, M.U. Islam, M.S. Awan, and Mukhtar Ahmad (Submitted January 14, 2013; in revised form March 21, 2013) Single-phase Cr-Ga-substituted BaM hexaferrites with chemical formula BaCrxGaxFe1222xO19 (x = 0.0, 0.1, 0.2, 0.3, and 0.4) are synthesized by means of a sol-gel autocombustion technique. Cold isostaticpressing technique has been used to press the as-prepared powders into pellets. Room-temperature DC resistivity enhances with the substitution of Cr-Ga contents. The temperature dependence of the DC resistivity shows the semiconducting nature. The dielectric constant and dielectric tangent loss decrease, while AC conductivity increases with the increasing applied eld frequency in the range of 1 MHz-3 GHz consistent with Koops theory and Maxwell-Wagners bi-layer model. The magnetic loss enhances, while the reection coefcient decreases with the increase of frequency as well as with the increase of Cr-Ga contents. Owing to improved properties, these materials are potential candidates for high-frequency applications in GHz range.

Keywords

AC conductivity, DC resistivity, dielectric constant, dielectric tangent loss, hexaferrites

1. Introduction
M-type hexaferrites MFe12O19 (M = Ba, Sr) are very important ferromagnetic oxides. These materials are useful for applications such as permanent magnets, high density recording media, and as components in microwave devices because of their higher intrinsic coercivity, large crystal anisotropy, and low cost. These materials are very stable at high frequencies because of high electric resistivity (Ref 1, 2). The dielectric properties of ferrites depend on various factors such as method of preparation, chemical composition, microstructure and the amount and type of the substitution (Ref 3). Ferrites are used at microwave frequencies because of high magnetocrystalline anisotropy which resulted in very low residual losses (Ref 4-7). Spineltype ferrites are limited in the applied frequency range because of their Snoeks limit is very much small because of imaginary part of the permeability that is considerably lowered in GHz range (Ref 2). The natural resonance occurs in the GHz range because of their in-plane anisotropy and therefore, it is possible to use these materials as high-frequency absorber (Ref 7-9). M-type hexaferrites are special type of absorbing materials because of their dielectric and magnetic losses in microwave frequency range. The essential conditions required to be satised by lossy materials are, the matching of characteristic impedance with intrinsic impedance of free space is the rst
Ihsan Ali, M.U. Islam, and Mukhtar Ahmad, Department of Physics, Bahauddin Zakariya University, Multan 60800, Pakistan; and M.S. Awan, Center for Micro and Nano Devices, Department of Physics, COMSATS Institute of Information Technology, Islamabad, Pakistan. Contact e-mails: ihsanali.ap@gmail.com and muislampk@ yahoo.com.

condition. This makes the dielectric constant and magnetic permeability of the material equal to each other. Second, the incident electromagnetic waves must enter and be attenuated rapidly through the material layer, thus reducing the emerging wave to an acceptably low magnitude (Ref 9, 10). The effects of Cr-Ga substitution on the structural and magnetic properties of hexaferrites (BaFe12O19) synthesized by sol-gel autocombustion route have already been reported in our recent publication (Ref 11). No comprehensive report about the electric and dielectric properties of BaCrxGaxFe122xO19 (x = 0.0-0.4) hexaferrites has been sighted in the literature to the best of our knowledge. The major aim of the present study is to enhance the electric and dielectric properties of single-phase BaM hexaferrites to make them suitable for high-frequency applications such as microwave radiations absorption, radar absorbing purposes, camouaging and attenuations of electromagnetic interference.

2. Materials and Methods

M-type hexaferrites with nominal composition BaCrxGax Fe122xO19 (x = 0.0-0.4) were synthesized using the sol-gel autocombustion technique. The calculated amounts of starting materials Ba(NO3)2 (99%, Sigma Aldrich), Fe(NO3)39H2O (98%, Applichem), Cr(NO3)34H2O (99%, Sigma Aldrich), Ga(NO3)34H2O (99.9%, Sigma Aldrich) and ammonia solution (Riedel-Dehaen, 33%) were dissolved in minimum amount of de-ionized water in a 1000 mL Pyrex beaker. The Citric acid was added into the prepared aqueous solution and kept the molar ratio between metal and citric acid 1:1. The pH value of the solution was maintained at about 7 using the ammonia solution. The solution was continuously stirred and heated at a constant temperature of 80 C on a hot plate magnetic stirrer. The solution was slowly evaporated until the mixture turned into a viscous gel. The temperature of the hot plate magnetic stirrer was increased up to about 200 C for the ignition of the

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gel. The gel was burnt in a self-propagating combustion manner until it was burnt out completely into a brown colored uffy powder. The sintering of the powder samples was carried out at 1000 C for 2 h in a digitally controlled programmable furnace to produce the required hexagonal phase. The powder samples were pressed into pellets of diameter 12-mm using the cold isostatic-pressing (CIP) technique. It is an excellent technique for preparing high-density pellets. Water was used as a medium for pressing. The CIP applies pressure from multiple directions for achieving greater uniformity of compaction and increased shape capability as compared with uniaxial pressing. First, the pressing of the powder samples was done uniaxially and then for further densication they were subjected to isostatic pressing at a pressure of 2000 bar. Room-temperature and temperature-dependent DC resistivity was measured using the two-point probe method. The AC conductivity and dielectric properties of samples were measured at room temperature using an Agilent impedance analyzer model E4991A RF in the frequency range (1 MHz-3 GHz). The AC conductivity (rAC) of the samples was calculated from the dielectric data using the following relation: rAC xe0 e00 xe0 e0 tan d Eq 1
0.06

x=0.3 x = 0.0 x = 0.1 x = 0.2 x = 0.3 x = 0.4 x=0.2

0.05

AC conductivity AC (ohm-cm)-1

0.04

0.03

x=0.4 x=0.1

0.02

0.01

x=0.0

0.00

-0.01 0.0 500.0M 1.0G 1.5G 2.0G 2.5G 3.0G

Frequency (GHz)

Fig. 1 Frequency-dependent AC conductivity (rac) of hexaferrites BaCrxGaxFe122xO19 (x = 0.0-0.4) at room temperature (293 K)

where x = 2pf represents the angular frequency, and e0 indicates the permittivity of free space (Ref 12). The complex impedance can be calculated from the relation: Z x Z 0 x Z 00 x Eq 2

where, Z and Z are real (resistive) and imaginary (reactive) parts of impedance. The electric modulus M*(x) is represented in the complex modulus form (Ref 13). M x where M 0 x M 00 x e0 x e0 x2 e00 x2 e00 x e0 x2 e00 x2 : Eq 4 1 M 0 x M 00 x e0 x je00 x Eq 3

model and Koops phenomenological theory, the ferrite materials consist of conducting grains separated by highly resistive thin layers of grain boundaries. Our results of AC conductivity showed that the grain boundaries contribute at low-frequency, but the dispersion trend at higher frequency may be attributed to the conducting nature of grains (Ref 14, 15). Several resonance peaks appeared in the plots of AC conductivity versus frequency as shown in the Fig. 1. The peaking nature occurred when the jumping frequency of electrons between Fe2+ and Fe3+ become equal to the frequency of applied AC eld (Ref 16, 17). According to Rezlescus model, the relaxation peaks occurred because of the collective contribution of both n- and p-type charge carriers (Ref 18). The transfer of ntype charges in ferrites is because of the hopping of electrons between Fe2+ and Fe3+ ions in accordance with the following phenomenon: Fe3 e $ Fe2 : Eq 6

Eq 5

Both types of charge carriers take part in the conduction process. The condition for observing a maximum in the dielectric loss of a material is xmax s 1 Eq 7

3. Results and Discussion

3.1 Electric Properties
3.1.1 High-Frequency Dependence of AC Electric Conductivity (rAC). Figure 1 shows the variation of AC electric conductivity (rAC) at room temperature for highfrequency range of 1 MHz-3 GHz. The AC conductivity (rAC) was calculated using the relation 1. The AC conductivity depends on electron hopping between Fe3+ and Fe2+ ions at the octahedral site. The AC conductivity (rAC) gradually enhanced with the increasing applied eld frequency. The frequency of electrons hopping between charge carriers Fe3+ and Fe2+ increased with the increasing applied eld frequency and hence AC conductivity (rAC) enhanced. The liberated charge and electron hopping both played a major role for the conduction mechanism in ferrites (Ref 12). According to Maxwell-Wagner

where xmax = 2pfmax. The relaxation time s is associated with the jumping probability per unit time p as 1 s p: 2 Eq 8

According to the Eq 8, the Debye relaxation process occurs when the jumping rate or rate of hopping of electrons between Fe2+ and Fe3+ becomes nearly equal to the frequency of the applied AC eld and this phenomenon is known as resonance (Ref 19, 20). 3.1.2 Room-Temperature DC Electric Resistivity (qRT). Figure 2 shows the variation of DC electric resistivity (qRT) at room temperature as a function of Cr-Ga content. The DC resistivity enhanced with the increasing Cr-Ga contents. The conduction in ferrites occurs because of hopping of electrons between Fe2+ and Fe3+ ions at the octahedral sites. It is reported that Cr and Ga preferentially occupy the octahedral

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8x10
9

7x10

6x10

5x10

4x10

3x10

2x10

0.0

0.1

0.2

0.3

0.4

Cr-Ga contents

nominal composition BaCr0.3Ga0.3Fe11.4O19 (x = 0.3) is the best one aamong all the synthesized samples because at this composition the DC resistivity approached to a maximum value of 7.72 9 109 X cm. The synthesized materials may be useful for reducing the eddy current losses at higher frequencies because of enhancement in the value of DC resistivity. The synthesized materials may fulll the requirements of their use in MLCI applications because of enhancement of DC resistivity greater than 108 X cm (Ref 28). 3.1.3 Temperature-Dependent DC Electric Resistivity. The temperature-dependent DC electric resistivity (q) was measured in the temperature range of 293-460 K. Figure 3 shows the variation of DC resistivity with the rise of temperature. The DC resistivity (q) decreased with the rise of temperature which showed the semiconducting nature that can be attributed to increase in drift mobility of charge carriers. The activation energy (Ea) was determined from the slope of linear plots of log q versus 1000/T (k1) (Ref 29). q q0 expEa =kB T Eq 11

Fig. 2 Composition-dependent DC resistivity of hexaferrites BaCrx GaxFe122xO19 (x = 0.0-0.4) at room temperature (293 K)

D.C resistivity RT (ohm-cm)

sites (Ref 21, 22). The number of Fe ions on the octahedral sites reduced because of the replacement of iron Fe3+ ions by chromium and gallium ions, and hence the hopping of electrons between Fe2+ and Fe3+ ions decreased. The improvement in resistivity may be due to decrease of charge carriers hopping from one site to another. The enhancement in resistivity may also be because of number of factors. The electronic conduction in hexaferrites is mainly because of hopping of electrons between ions of the same element present in more than one valence states. M-type hexaferrite crystallizes in a hexagonal structure with 64 ions per unit cell on 11 different symmetry sites. The 24 Fe3+ atoms are distributed over ve distinct sites: three octahedral sites (12k, 2a and 4f2), one tetrahedral (4f1) site and one bipyramidal site (2b) (Ref 23). The distance between two metal ions at octahedral sites is smaller than the distance between a metal ion at octahedral site and another metal ion at tetrahedral site. Therefore, the probability of hopping between tetrahedral and octahedral sites under normal circumstances may be very small than that of the hopping between octahedraloctahedral sites. The hopping does not occur between tetrahedral-tetrahedral sites because there are only ferric (Fe3+) ions at the tetrahedral sites and any ferrous (Fe2+) ions formed during sintering process prefer to occupy octahedral sites (Ref 24). The conduction in ferrites is mainly because of hopping of electrons from ferric (Fe3+) to ferrous (Fe2+) ions at octahedral sites, i.e., Fe3+-O-Fe2+ (Ref 24-26). The following reactions show the number and mobility of holes: Fe3 e ! Fe2 O 2 2 e ! O : Eq 9 Eq 10

3+

where q is the resistivity at temperature T, q0 is the resistivity at 1/T = 0, Ea is the activation energy, and kB is the Boltzmanns constant. The activation energy was enhanced with the increasing Cr-Ga contents as shown in Table 1. The activation energy (Ea) and DC electric resistivity (q) at room temperature indicate the increasing trend as shown in Fig. 4. The increase in resistivity expected because of the increase in activation energy, because the sample with high activation energy has high value of resistivity and vice versa (Ref 30). The activation energy is maximum that is 0.263 eV at x = 0.0 (BaCr0.3Ga0.3Fe11.4O19). The drift mobility (ld) of the materials was determined using the following relation (Ref 31): ld 1=geq: Eq 12

where e is the charge on an electron, q is the resistivity at room temperature, and g represents the contents of charge carriers. The contents of charge carriers g were calculated from the following relation (Ref 32). g Na db PFe =M : Eq 13

where M is the molecular weight, Na is the Avogadro number (6.02 9 1023/mole), db is the bulk density of the samples, and PFe is the number of iron atoms present in the chemical formula of oxide. The mobility of materials decreased with the increasing Cr-Ga contents as shown in Table 1. The materials of higher resistivity have lower mobility and vice versa (Ref 33). The drift mobility of a sample with composition BaCr0.3Ga0.3Fe11.4O19 decreased to a minimum value of 0.263 eV.

3.2 High-Frequency Dependence of Dielectric Properties

3.2.1 High-Frequency Dependence of Dielectric Constant (e) and Loss Tangent ( tan d). Figures 4 and 5 show the variation of dielectric constant (e) and loss tangent ( tan d) versus frequency of M-type hexaferrites BaCrxGaxFe122xO19 (x = 0.0-0.4) at room temperature, respectively, in the frequency range of 1 MHz-3 GHz. M-type hexaferrite materials are highly resistive and are important for low dielectric loss. The values of dielectric parameters (e, tan d) are higher at lower frequencies as compared with higher frequencies. The higher values of dielectric parameters (e, tan d) at lower frequencies may be attributed to inhomogeneity in hexaferrite structure, i.e., Fe2+ ions, voids, interfacial dislocations and

The mobility and concentration of holes decreased and as a result the DC electric resistivity enhanced (Ref 25). The roomtemperature DC resistivity experiences a signicant improvement from a value of 2.55 9 109 to 7.72 9 109 X cm and then dropped upon increasing the Cr-Ga contents further as shown in Table 1. This behavior of resistivity is because of redistribution of cations on the lattice sites. The DC resistivity of M-type hexaferrites measured at room temperature by different researchers was found to lie in the range of 104-107 X cm (Ref 26, 27). However, in the present study, the material with

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Table 1 AC electric conductivity (rAC), DC resistivity (qRT), activation energy (Ea), drift mobility (ld), dielectric constant (e), dielectric tangent loss ( tan d) and dielectric loss factor (e) of BaCrxGaxFe1222xO19 (x = 0.0-0.4) hexaferrites
Parameters rac 9 103 (X cm)1 at 500 MHz rac 9 102 (X cm)1 at 3 GHz qRT (X cm) 9 109 at 293 K ld (cm2/V s) 9 1013 at 293 K e at 3 GHz Tand at 3 GHz e at 3 GHz x = 0.0 0.49 0.24 2.55 9.2 3.77 0.01 0.01 x = 0.1 3.36 1.87 4.72 4.9 3.00 0.04 0.12 x = 0.2 6.87 3.94 5.84 4.0 3.44 0.07 0.26 x = 0.3 10.1 5.16 7.72 3.0 3.26 0.07 0.22 x = 0.4 7.08 3.68 7.36 3.2 2.30 0.01 0.16

10.0 9.5 9.0

9.0

Dielectric constant ()

(ohm-cm)

x=0.0 x=0.1 x=0.2 x=0.3 x=0.4

8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0

x=0.0 x=0.1 x=0.2 x=0.3 x=0.4

8.5 8.0 7.5 7.0 6.5 6.0 2.2 2.4 2.6 2.8 3.0
-1

''

Log

x=0.0 x=0.2 x=0.4 x=0.1 x=0.3

3.2

3.4

3.6
0.0 500.0M 1.0G 1.5G 2.0G 2.5G 3.0G

1000/T (K )

Frequency (GHz)

Fig. 3 Variation of DC resistivity ( log q) with inverse of temperature (1000/T) for hexaferrites BaCrxGaxFe122xO19 (x = 0.0-0.4)

Fig. 4 Frequency-dependent dielectric constant (e) of BaCrxGax Fe122xO19 (x = 0.0-0.4) hexaferrites at room temperature

grain boundary defects etc. (Ref 34). The higher dielectric constant at lower frequencies reduces the penetration depth of electromagnetic waves by increasing the skin effect. The general behavior for all samples is the decrease of dielectric parameters (e, tan d) with the increasing frequency because of very fast variations of the applied uctuating electric eld. These parameters (e, tan d) decreased sharply at lower frequency and slowly at higher frequency. The values of these parameters became almost constant at further higher frequencies. The reduction in dielectric constant (e) with the increasing frequency is a normal ferromagnetic behavior for hexaferrites. The observed variations are consistent with Koops theory and Maxwell-Wagner bi-layer model (Ref 14). According to this model, the dielectric structure of ferrites consists of conducting grains separated by a layer of insulating grain-boundaries, which offer opposition to the conduction process. The grain boundaries formed during the sintering process because of the supercial reduction or oxidation of crystallites in the porous samples because of their direct contact with the ring atmosphere (Ref 35). The electrons approach the grain boundaries by hopping. If the resistance of a grain boundary is high, then the charge carriers align themselves at the grain boundaries and as a result polarization of the dielectric material occurs that increase the dielectric parameters (e, tan d) (Ref 36). The dispersion phenomenon can be explained on the basis of hopping of electrons between Fe2+ and Fe3+ ions. The phenomenon of dielectric polarization is similar as the electric conduction which is in agreement with the strong correlation

between the conduction mechanism and dielectric behavior of ferrites as established by Iwauchi (Ref 37) and Rezlescu (Ref 19). The displacement of charge carriers occurred in the direction of an applied electric eld because of electronic exchange, i.e., Fe2+ Fe3+ + e1, which is responsible for the polarization. The electrons follow the change in applied electric eld as long as the time required for hopping is less than the alternating time period of the applied electric eld and this may be the main cause for the dispersion in M-type hexaferrites. The reduction in polarization with the increasing applied eld frequency is because of the reason that electronic exchange between the charge carriers cannot respond the alternating eld beyond certain applied frequencies because of the smaller relaxation time and ultimately it becomes independent of it. The chances of electrons to approach the grain boundaries become very low. This disrupts the polarization buildup in the material and decreased the dielectric parameters (e, tan d) with the increasing frequency (Ref 38). The dielectric tangent loss ( tan d) depends on different factors such as stoichiometry, types and number of charge carriers, etc., which in turn depends on synthesis technique, composition and sintering temperature of the materials (Ref 39). The dielectric losses in hexaferrites also depend on the conductivity where the materials of high conductivity exhibit high losses and vice versa (Ref 40). The hexaferrite materials are anisotropic and have a higher value of intrinsic magnetocrystalline anisotropy eld as compared with the spinel ferrites and garnets. The natural resonance occurs in the GHz region because of their in-plane anisotropy. Moreover,

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0.24 0.22 0.20

x=0.4

0.24
x = 0.0 x = 0.1 x = 0.2 x = 0.3 x = 0.4

x=0.4

0.22 0.20

Dielectric tangent loss (Tan)

Dielectric loss factor ('')

0.18 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 -0.02

x=0.3 x=0.2 x=0.1

0.18 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0.00 -0.02 0.0 500.0M 1.0G 1.5G 2.0G 2.5G

x=0.2

x=0.3

x = 0.0 x = 0.1 x = 0.2 x = 0.3 x = 0.4

x=0.1 x=0.0

x=0.0

3.0G

0.0

500.0M

1.0G

1.5G

2.0G

2.5G

3.0G

Frequency (GHz)

Frequency (GHz)

Fig. 5 Frequency-dependent (1 MHz-3 GHz) dielectric tangent loss ( tan d) of BaCrxGaxFe122xO19 (x = 0.0-0.4) hexaferrites at room temperature

Fig. 6 Frequency-dependent (1 MHz-3 GHz) dielectric loss factor (e) for BaCrxGaxFe122xO19 (x = 0.0-0.4) hexaferrites vs. applied eld frequency at room temperature

the peaks shift toward lower frequency region with the increasing Cr-Ga contents. The shifting of the resonance peaks toward lower frequencies region shows a decrease of the resonance frequency. The synthesized materials because of low dielectric constant for higher frequency range may be useful for high-frequency applications such as in microwave devices because these devices require highly resistive materials. Therefore, these nanomaterials may be used as high-frequency absorber (Ref 7-9). 3.2.2 High-Frequency Dependence of Dielectric Loss Factor (e). Figure 6 shows the prole of dielectric loss factor (e) at room temperature as a function of applied eld frequency in the range of 1 MHz-3 GHz. The dielectric loss factor was calculated using the relation e00 e0 tan d (Ref 41), which reduced with increasing the applied eld frequency. The dissipation factor directly depends on the value of loss tangent ( tan d). The polarization response increasingly lagging-behind the applied electric eld as the frequency of applied eld reaches the relaxation frequency. The internal friction hindered the movement of each dipole, which leads to heating in the sample and power loss. The power loss in dielectric materials may be because of work done to overcome the frictional damping forces acting on the dipole during their rotation. The dielectric loss is an essential part of the total core loss in hexaferrites. This power loss may be very much signicant at applied electric eld frequencies nearer to the vicinity of relaxation frequencies for each dipole for a particular dielectric material (Ref 42). 3.2.3 Composition Dependence of Dielectric Parameters (e, e and tan d). Table 1 shows the composition dependence of dielectric constant (e), loss tangent ( tan d) and loss factor (e) at a particular frequency of 3 GHz. The dielectric constant values of all samples continuously decreased, while the values of dielectric loss tangent tan d (e) and loss factor (e) increased with the increasing Cr-Ga contents. The conduction mechanism in these ferrites is based on the hopping of electrons between ferric (Fe3+) and ferrous (Fe2+) ions at the octahedral sites. It is already reported (Ref 21, 22) that the Cr and Ga ions preferentially occupy the octahedral sites. The total number

of Fe3+ ions on the octahedral sites in the M-type hexaferrite lattice decreased because of the replacement of Fe3+ ions by the Cr-Ga ions, and hence the hopping of electrons between Fe2+ and Fe3+ ions also decreased. The decrease in dielectric constant and increase in loss tangent with the increasing Cr-Ga contents is suitable for high-frequency applications. 3.2.4 High-Frequency Dependence of Impedance. Figure 7 shows the real (Z) and complex (Z inset) impedance of the hexaferrites BaCrxGaxFe122xO19 (x = 0.0-0.4) at room temperature as a function of applied eld frequency in the range of 1 MHz-3 GHz. It is observed that both Z and Z showed a decreasing behavior and exhibited the possibility of increase in AC conductivity with the increasing applied eld frequency. The impedance in the higher-frequency region suggested a possible release of space charge and lowering of the barrier properties in the materials (Ref 43). Figure 7 inset shows that some peaks are also appeared in the prole of Z versus frequency. The complex parts of impedance (Z) almost became independent from frequency for higher frequencies region (Ref 44). Moreover, the position of the peaks shifted toward the lower frequencies region with the increasing Cr-Ga contents. The low frequency dislocation of the relaxation peak may represent the region of frequencies in which ions can perform successful hopping from one site to the other neighboring site. The higher frequency Z peak may indicate the range of frequencies in which the ions are conned to their potential wells and can make localized motion within the well (Ref 45). 3.2.5 High-Frequency Dependence of Electric Modulus. Figure 8 shows the variation of real part of modulus (M) at room temperature as a function of applied eld frequency in the range of 1 MHz-3 GHz. The complex electric modulus is a very signicant tool to determine, interpret and analyze the electric transport mechanism in the hexaferrite materials. The real part of the complex modulus (M) was calculated using the relation (Ref 4). It is observed that the value of M is smaller in the lower frequency region. The value of (M) increased and approached to a maximum constant value for higher frequencies which may be attributed to a lack of restoring force responsible for the mobility of ions/carriers under the inuence

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80
Complex impedance Z" (ohm)

x=0.4
70

x=0.1

Real part of impedance 'Z' (ohm)

x=0.1

60

x=0.0

Real part of complex modulus (M')

-77 -78 -79 -80 -81 -82 -83 -84 -85 -86 -87 -88 -89 -90 -91 -92 -93

x=0.4

x=0.2

x=0.3

x = 0.0 x = 0.1 x = 0.2 x = 0.3 x = 0.4

x=0.0
50 40 30 20 10 0 1.8G
x = 0.0 x = 0.1 x = 0.2 x = 0.3 x = 0.4

0.0

500.0M

1.0G

1.5G

2.0G

2.5G

3.0G

Frequency (GHz)

x=0.3

x=0.2

0.48 0.46 0.44 0.42 0.40 0.38 0.36 0.34 0.32 0.30 0.28 0.26 0.24 0.22 0.20 0.18 0.16 0.14 0.12 0.10

x=0.4 x=0.3 x=0.0

x=0.2
Imaginary part of complex modulus
0.070 0.065 0.060 0.055 0.050 0.045 0.040 0.035 0.030 0.025 0.020 0.015 0.010 0.005 0.000 -0.005 -0.010 -0.015 -0.020 0.0 x=0.4

x=0.1
x = 0.0 x = 0.1 x = 0.2 x = 0.3 x = 0.4 0.0 500.0M 1.0G

x=0.3

x = 0.0 x = 0.1 x = 0.2 x = 0.3 x = 0.4

x=0.3

x=0.1

x=0.0

500.0M

1.0G

1.5G

2.0G

2.5G

3.0G

Frequency (GHz)

2.0G

2.2G

2.4G

2.6G

2.8G

3.0G

1.5G

2.0G

2.5G

3.0G

Frequency (GHz)

Frequency (GHz)

Fig. 7 Frequency-dependent real (Z) and complex (Z inset) impedance of BaCrxGaxFe122xO19 (x = 0.0-0.4) hexaferrites at room temperature

Fig. 8 Frequency-dependent complex modulus (M) and (M inset) of BaCrxGaxFe122xO19 (x = 0.0-0.4) hexaferrites at room temperature

of induced electric eld. This type of trend favors the conduction phenomena and may be because of long-range mobility of charge carriers (Ref 46). Figure 8 inset shows the variation of imaginary part (M) of the complex modulus versus applied eld frequency at room temperature. The imaginary part of complex modulus (M) was calculated using the relation (Ref 5). The values of M were also higher in the lower frequency region and decreased with the increasing frequency. The observed behavior of the complex modulus (M) is because of the same reasons as mentioned for the variation of dielectric loss factor (e).

3.3 Microwave Absorption Properties

Figure 9 shows the variation of magnetic loss tangent tan dl of M-type hexaferrites BaCrxGaxFe122xO19 (x = 0.0, 0.2, 0.3) at room temperature as a function of applied eld frequency in the range of 1 MHz-3 GHz . It also shows the variation of magnetic loss tangent tan dl with the increasing Cr-Ga contents. It is observed that the magnetic loss tangent tan dl enhanced with the increasing frequency for all the samples (x = 0.0, 0.2, 0.3). The magnetic loss tangent tan dl continuously increased with the increasing Cr-Ga concentration as shown in Fig. 9. The magnetic loss tangent tan dl for the substituted samples (x = 0.2, 0.3) is higher than that of the unsubstituted one (x = 0.0). The microwave absorbing materials are characterized by the permittivity (e = e je) and permeability (l = l jl). The imaginary parts such as e and l account for the microwave energy loss in the materials. In fact, the loss is the conversion of electromagnetic wave energy into heat. The microwave absorbing materials are coated on the metallic structures to reduce the scattering. There are two necessary requirements for low reection. The rst requirement is that the reection of incident electromagnetic waves penetrating into the material should be lowest. The second requirement is that the material should absorb the maximum amount of electromagnetic waves. In order to fulll the rst requirement, the impedance match between the material and free space is required, i.e., le = 1, where l and e are the complex permeability and permittivity of the absorbing mate-

rial, respectively. Usually, the permeability l is very much smaller than e at microwave frequency for most of the electromagnetic materials. The permeability l should increase and e should decrease to satisfy the impedance match. Second, the synthesized material should have higher imaginary part of permittivity e or permeability l at microwave frequency to effectively absorb the incident electromagnetic wave. Therefore, the electromagnetic materials with excellent absorbing ability should have high permeability l, small permittivity e, and large magnetic or dielectric loss at microwave frequency. According to transmission line theory, the reection coefcient RL (dB) of electromagnetic wave, under perpendicular wave incidence at the surface of a single-layer material backed by a perfect conductor can be dened by the equation (Ref 47): RL dB 20 log10 Zin Z0 Zin Z0 ! Eq 14

where Z0 = 377 X, the characteristic impedance of free space and is given by Z0 r l0 : e0 Eq 15

For a microwave absorbing layer terminated by a short circuit, the normalized input impedance (Zin) at the air-absorber interface is represented by (Ref 48) !  r  lr 2pft p tanh j Eq 16 lr er Zin Z0 c er where lr = l jl and er = e je complex permeability and complex permittivity respectively, for the absorber medium, f is the frequency, c is the velocity of light, and t is the thickness of samples. The conditions for impedance matching at which Zin becomes equal to Z0 are satised at particular matching thickness (tm) and matching frequency (fm). The reection loss is measured at the optimum values of the matching thickness (tm) determined earlier (Ref 49) which is expressed by the following equation:

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0.20 0.18 0.16 0.14
1.08

Ga=0.0 Ga=0.2 Ga=0.3

x=0.3
1.06 1.04

x=0.2
Reflection coefficient

x=0.0 x=0.2 x=0.3

x=0.0

1.02 1.00 0.98 0.96 0.94 0.92 0.90 0.88

Magnetic loss tangent

0.12 0.10 0.08 0.06 0.04 0.02 0.00

x=0.0

2.5 GHz x=0.2 x=0.3

0.0 500.0M 1.0G 1.5G 2.0G 2.5G 3.0G

0.86

-0.02 -0.04 0.0 500.0M 1.0G 1.5G 2.0G 2.5G 3.0G

0.84

Frequency (GHz)

Frequency (GHz)

Fig. 9 Frequency-dependent (1 MHz-3 GHz) magnetic loss tangent tan dl for BaCrxGaxFe122xO19 (x = 0.0-0.4) hexaferrites at room temperature

Fig. 10 Frequency-dependent (1 MHz-3 GHz) reection coefcient (C) for BaCrxGaxFe122xO19 (x = 0.0, 0.2, 0.3) hexaferrites at room temperature

4. Conclusions
tm ka c p 4f lr er 4 Eq 17 An economic and simple technique sol-gel autocombustion has been used to synthesize the Cr-Ga-substituted BaM hexaferrites. DC resistivity improves, while drift mobility drops with the increase of Cr-Ga contents. The maximum value of the DC resistivity is observed for the sample (x = 0.3). The temperature-dependent DC resistivity exhibits the semiconducting nature. The dielectric constant and tangent loss tan de decrease with the increase of applied eld frequency in the range of 1 MHz-3 GHz. The samples substituted with Cr-Ga contents have lower values of dielectric constant and higher values of loss tangent compared with the unsubstituted sample. AC conductivity (rAC) enhances with the increase of the applied eld frequency. The magnetic loss tangent tan dl continuously improves with the increase of applied eld frequency as well as with the increase of Cr-Ga contents. The synthesized M-type hexaferrite materials are excellent materials for high-frequency applications, such as microwave radiations absorption, camouaging, and attenuations of electromagnetic interference because of their enhanced electric resistivity, large magnetic or dielectric loss, and reduction of dielectric constant and reection loss at microwave frequency.

where ka is the wavelength inside the absorber, f is the incident frequency of free space. This equation shows that when the thickness of absorber is equal to one quarter of wavelength, the wave reected at the air-absorber interface is out of phase with the wave reected at absorber-metal interface hence satisfying the quarter-wave thickness criteria. The wide absorption bandwidths and low reection loss peaks make the materials useful for microwave applications. Figure 10 shows high-frequency 1 MHz-3 GHz-dependent reection coefcient (C) for the M-type BaCrxGaxFe122xO19 (x = 0.0, 0.2, 0.3) hexaferrites at room temperature. It is observed that the reection coefcient (C) is decreased with the increase of applied eld frequency. The reection coefcient (C) is also reduced with the increase of Cr-Ga contents. The absorption peak appeared for the unsubstituted sample (x = 0.0) at a particular frequency of 2.5 GHz as shown in Fig. 10. The peaking nature occurs because of resonance when the jumping frequency of electrons between Fe2+ and Fe3+ become equal to the frequency of applied AC eld (Ref 16, 17). The appearance of such absorption peaks for the substituted samples (x = 0.2, 0.3) are also expected in the frequency range greater than 3 GHz, because the shifting of peaks occurs with the increasing Cr-Ga contents. The similar trend was also observed earlier in the case of M-type barium hexaferrites (Ref 49). A good microwave absorption material needs to have low reection loss, wide absorption bandwidth, and low matching thickness. There exists no ideal material which fullls all these requirements. However, in the present study, the reection coefcient decreased with the increasing applied eld frequency as well as with the increasing Cr-Ga contents. Hence, the synthesized materials can be considered as potential candidates for high-frequency applications such as microwave radiations absorption, camouaging, and attenuations of electromagnetic interference.

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