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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Author's personal copy JMEPEG DOI: 10. Ga(NO3)3Æ4H2O (99. while the reflection coefficient decreases with the increase of frequency as well as with the increase of Cr-Ga contents.9%. Department of Physics. 2).0-0. Islam. 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). Keywords AC conductivity. hexaferrites 1. Sigma Aldrich). Cold isostaticpressing technique has been used to press the as-prepared powders into pellets. in revised form March 21. This makes the dielectric constant and magnetic permeability of the material equal to each other. The magnetic loss enhances. and Mukhtar Ahmad (Submitted January 14. The Citric acid was added into the prepared aqueous solution and kept the molar ratio between metal and citric acid 1:1. Applichem). 33%) were dissolved in minimum amount of de-ionized water in a 1000 mL Pyrex beaker. The essential conditions required to be satisfied by lossy materials are. 0. Room-temperature DC resistivity enhances with the substitution of Cr-Ga contents. The pH value of the solution was maintained at about 7 using the ammonia solution. thus reducing the emerging wave to an acceptably low magnitude (Ref 9.U.com and muislampk@ yahoo.4) are synthesized by means of a sol-gel autocombustion technique. These materials are useful for applications such as permanent magnets. Awan. these materials are potential candidates for high-frequency applications in GHz range. Introduction M-type hexaferrites MFe12O19 (M = Ba. the incident electromagnetic waves must enter and be attenuated rapidly through the material layer.1. Spineltype ferrites are limited in the applied frequency range because of their SnoekÕs limit is very much small because of imaginary part of the permeability that is considerably lowered in GHz range (Ref 2).com. Sigma Aldrich). The solution was continuously stirred and heated at a constant temperature of 80 °C on a hot plate magnetic stirrer. and as components in microwave devices because of their higher intrinsic coercivity. Fe(NO3)3Æ9H2O (98%. 0. 0.1007/s11665-013-0562-7 ÓASM International 1059-9495/$19.S. The dielectric properties of ferrites depend on various factors such as method of preparation. COMSATS Institute of Information Technology. condition. Second. camouflaging and attenuations of electromagnetic interference.ap@gmail.0. 10). Pakistan. Center for Micro and Nano Devices. Multan 60800. 2. The calculated amounts of starting materials Ba(NO3)2 (99%.S. Sr) are very important ferromagnetic oxides. Cr(NO3)3Æ4H2O (99%.3. and low cost. The natural resonance occurs in the GHz range because of their in-plane anisotropy and therefore. DC resistivity. 2013. and M. The dielectric constant and dielectric tangent loss decrease. microstructure and the amount and type of the substitution (Ref 3). Sigma Aldrich) and ammonia solution (Riedel-Dehaen.4) hexaferrites has been sighted in the literature to the best of our knowledge. M. The solution was slowly evaporated until the mixture turned into a viscous gel. the matching of characteristic impedance with intrinsic impedance of free space is the first Ihsan Ali. The temperature dependence of the DC resistivity shows the semiconducting nature. Department of Physics. Ferrites are used at microwave frequencies because of high magnetocrystalline anisotropy which resulted in very low residual losses (Ref 4-7).2. Islam. 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. M. Bahauddin Zakariya University. Islamabad.4) were synthesized using the sol-gel autocombustion technique.0-0. large crystal anisotropy. Contact e-mails: ihsanali. Owing to improved properties. M. high density recording media. while AC conductivity increases with the increasing applied field frequency in the range of 1 MHz-3 GHz consistent with KoopÕs theory and Maxwell-WagnerÕs bi-layer model. radar absorbing purposes. dielectric tangent loss. Materials and Methods M-type hexaferrites with nominal composition BaCrxGax Fe12À2xO19 (x = 0. chemical composition. M-type hexaferrites are special type of absorbing materials because of their dielectric and magnetic losses in microwave frequency range. The temperature of the hot plate magnetic stirrer was increased up to about 200 °C for the ignition of the Journal of Materials Engineering and Performance . 2013) Single-phase Cr-Ga-substituted BaM hexaferrites with chemical formula BaCrxGaxFe1222xO19 (x = 0. and Mukhtar Ahmad. it is possible to use these materials as high-frequency absorber (Ref 7-9). dielectric constant. These materials are very stable at high frequencies because of high electric resistivity (Ref 1.00 Electric and Dielectric Properties of Cr-Ga Substituted BaM Hexaferrites for High-Frequency Applications Ihsan Ali.U. Pakistan. No comprehensive report about the electric and dielectric properties of BaCrxGaxFe12À2xO19 (x = 0. and 0. Awan.

Water was used as a medium for pressing. According to RezlescuÕs model. The conduction in ferrites occurs because of hopping of electrons between Fe2+ and Fe3+ ions at the octahedral sites.2 Room-Temperature DC Electric Resistivity (qRT).1 x = 0. Figure 2 shows the variation of DC electric resistivity (qRT) at room temperature as a function of Cr-Ga content. Figure 1 shows the variation of AC electric conductivity (rAC) at room temperature for highfrequency range of 1 MHz-3 GHz.04 0. Room-temperature and temperature-dependent DC resistivity was measured using the two-point probe method. The AC conductivity depends on electron hopping between Fe3+ and Fe2+ ions at the octahedral site. 1. The peaking nature occurred when the jumping frequency of electrons between Fe2+ and Fe3+ become equal to the frequency of applied AC field (Ref 16. 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. According to Maxwell-Wagner where xmax = 2pfmax. 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). Z¢ and Z¢¢ are real (resistive) and imaginary (reactive) parts of impedance.0-0.1 0. Several resonance peaks appeared in the plots of AC conductivity versus frequency as shown in the Fig.4) at room temperature (293 K) where x = 2pf represents the angular frequency.00 -0. M à ðxÞ ¼ where M 0 ðxÞ ¼ M 00 ðxÞ ¼ e0 ðxÞ ½e0 ðxފ2 þ½e00 ðxފ2 e00 ðxÞ ½e0 ðxފ2 þ½e00 ðxފ2 : ðEq 4Þ 1 ¼ M 0 ðxÞ þ M 00 ðxÞ e0 ðxÞ À je00 ðxÞ ðEq 3Þ model and KoopÕs phenomenological theory. 3. The CIP applies pressure from multiple directions for achieving greater uniformity of compaction and increased shape capability as compared with uniaxial pressing.06 x=0.3 x = 0. The AC conductivity (rAC) gradually enhanced with the increasing applied field frequency. 15). First. The electric modulus M*(x) is represented in the complex modulus form (Ref 13).02 0.0M 1.0G 1. the pressing of the powder samples was done uniaxially and then for further densification they were subjected to isostatic pressing at a pressure of 2000 bar. Our results of AC conductivity showed that the grain boundaries contribute at low-frequency.2 0. the relaxation peaks occurred because of the collective contribution of both n.1 Electric Properties 3.1.5G 3. The condition for observing a maximum in the dielectric loss of a material is xmax s ¼ 1 ðEq 7Þ 3. 20).4 x=0.01 0. It is an excellent technique for preparing high-density pellets. and e0 indicates the permittivity of free space (Ref 12).2 x = 0.0 x = 0.and p-type charge carriers (Ref 18).1.0 500.0G 2.1 High-Frequency Dependence of AC Electric Conductivity (rAC). It is reported that Cr and Ga preferentially occupy the octahedral Journal of Materials Engineering and Performance .5G 2. The complex impedance can be calculated from the relation: Z à x ¼ Z 0 ðxÞ þ Z 00 ðxÞ ðEq 2Þ where. 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 field and this phenomenon is known as resonance (Ref 19. The powder samples were pressed into pellets of diameter 12-mm using the cold isostatic-pressing (CIP) technique.4 x=0. Results and Discussion 3. 17). The DC resistivity enhanced with the increasing Cr-Ga contents. The gel was burnt in a self-propagating combustion manner until it was burnt out completely into a brown colored fluffy powder.0G Frequency (GHz) Fig.3 x = 0.Author's personal copy gel.05 AC conductivity σAC (ohm-cm)-1 0. 1 Frequency-dependent AC conductivity (rac) of hexaferrites BaCrxGaxFe12À2xO19 (x = 0.03 x=0. The liberated charge and electron hopping both played a major role for the conduction mechanism in ferrites (Ref 12). the ferrite materials consist of conducting grains separated by highly resistive thin layers of grain boundaries. The relaxation time s is associated with the jumping probability per unit time p as 1 s ¼ p: 2 ðEq 8Þ According to the Eq 8. The frequency of electrons hopping between charge carriers Fe3+ and Fe2+ increased with the increasing applied field frequency and hence AC conductivity (rAC) enhanced.01 x=0. The AC conductivity (rAC) was calculated using the relation 1. 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: Fe3þ þ eÀ $ Fe2þ : ðEq 6Þ ðEq 5Þ Both types of charge carriers take part in the conduction process. but the dispersion trend at higher frequency may be attributed to the conducting nature of grains (Ref 14.0 0. The AC conductivity (rAC) of the samples was calculated from the dielectric data using the following relation: rAC ¼ xe0 e00 ¼ xe0 e0 tan d ðEq 1Þ 0.

q ¼ q0 expðEa =kB T Þ ðEq 11Þ Fig. 3.0 0.3) is the best one aamong all the synthesized samples because at this composition the DC resistivity approached to a maximum value of 7.4) at room temperature.4) at room temperature (293 K) D.4 Cr-Ga contents nominal composition BaCr0. Therefore.1 High-Frequency Dependence of Dielectric Constant (e¢) and Loss Tangent ( tan d). tan d) at lower frequencies may be attributed to inhomogeneity in hexaferrite structure. in the frequency range of 1 MHz-3 GHz. The synthesized materials may be useful for reducing the eddy current losses at higher frequencies because of enhancement in the value of DC resistivity.3 0.1. Ea is the activation energy. the probability of hopping between tetrahedral and octahedral sites under normal circumstances may be very small than that of the hopping between octahedraloctahedral sites.3Ga0. because the sample with high activation energy has high value of resistivity and vice versa (Ref 30). and g represents the contents of charge carriers. q is the resistivity at room temperature. The synthesized materials may fulfill the requirements of their use in MLCI applications because of enhancement of DC resistivity greater than 108 X cm (Ref 28). voids. and kB is the BoltzmannÕs constant. The temperature-dependent DC electric resistivity (q) was measured in the temperature range of 293-460 K. The improvement in resistivity may be due to decrease of charge carriers hopping from one site to another. This behavior of resistivity is because of redistribution of cations on the lattice sites.e. i. 27). and PFe is the number of iron atoms present in the chemical formula of oxide. the material with Journal of Materials Engineering and Performance . 22). The increase in resistivity expected because of the increase in activation energy. 4.3Fe11. 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 26.0-0.. The materials of higher resistivity have lower mobility and vice versa (Ref 33). 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 materials are highly resistive and are important for low dielectric loss.. Na is the Avogadro number (6.Author's personal copy 8x10 9 7x10 9 6x10 9 5x10 9 4x10 9 3x10 9 2x10 9 0.3Fe11.72 9 109 X cm and then dropped upon increasing the Cr-Ga contents further as shown in Table 1.e.0 (BaCr0. The enhancement in resistivity may also be because of number of factors. Figures 4 and 5 show the variation of dielectric constant (e¢) and loss tangent ( tan d) versus frequency of M-type hexaferrites BaCrxGaxFe12À2xO19 (x = 0. respectively. The activation energy (Ea) and DC electric resistivity (q) at room temperature indicate the increasing trend as shown in Fig. The drift mobility of a sample with composition BaCr0. Figure 3 shows the variation of DC resistivity with the rise of temperature.3Ga0.02 9 1023/mole). 2 Composition-dependent DC resistivity of hexaferrites BaCrx GaxFe12À2xO19 (x = 0. The number of Fe ions on the octahedral sites reduced because of the replacement of iron Fe3+ ions by chromium and gallium ions. 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. i. The 24 Fe3+ atoms are distributed over five distinct sites: three octahedral sites (12k. tan d) are higher at lower frequencies as compared with higher frequencies. interfacial dislocations and The mobility and concentration of holes decreased and as a result the DC electric resistivity enhanced (Ref 25). The conduction in ferrites is mainly because of hopping of electrons from ferric (Fe3+) to ferrous (Fe2+) ions at octahedral sites. db is the bulk density of the samples. The activation energy (Ea) was determined from the slope of linear plots of log q versus 1000/T (kÀ1) (Ref 29). 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 values of dielectric parameters (e¢. in the present study. The roomtemperature DC resistivity experiences a significant improvement from a value of 2. q0 is the resistivity at 1/T = 0. The higher values of dielectric parameters (e¢. Fe3+-O-Fe2+ (Ref 24-26). one tetrahedral (4f1) site and one bipyramidal site (2b) (Ref 23).2.263 eV at x = 0. However.3Ga0. Fe2+ ions.263 eV.2 High-Frequency Dependence of Dielectric Properties 3.55 9 109 to 7. and hence the hopping of electrons between Fe2+ and Fe3+ ions decreased. The contents of charge carrierÕs g were calculated from the following relation (Ref 32).3Fe11. The following reactions show the number and mobility of holes: Fe3þ þ eÀ ! Fe2þ O 2 À þ 2 eÀ ! O : ðEq 9Þ ðEq 10Þ 3+ where q is the resistivity at temperature T.4O19). The drift mobility (ld) of the materials was determined using the following relation (Ref 31): ld ¼ 1=geq: ðEq 12Þ where e is the charge on an electron. g ¼ Na db PFe =M : ðEq 13Þ where M is the molecular weight.4O19 (x = 0. 3.2 0. M-type hexaferrite crystallizes in a hexagonal structure with 64 ions per unit cell on 11 different symmetry sites.1 0. 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.4O19 decreased to a minimum value of 0. The activation energy was enhanced with the increasing Cr-Ga contents as shown in Table 1.3 Temperature-Dependent DC Electric Resistivity.0-0. The mobility of materials decreased with the increasing Cr-Ga contents as shown in Table 1.C resistivity ρRT (ohm-cm) sites (Ref 21. The activation energy is maximum that is 0.72 9 109 X cm. 2a and 4f2).

4 x=0.1 x=0.5G 3.0 7.0 7.00 0.87 3.16 7.9 3.0 6.5 5.26 x = 0. These parameters (e¢. tan d) (Ref 36). The general behavior for all samples is the decrease of dielectric parameters (e¢.12 x = 0.2 3. The values of these parameters became almost constant at further higher frequencies.04 0. The natural resonance occurs in the GHz region because of their in-plane anisotropy. 3 Variation of DC resistivity ( log q) with inverse of temperature (1000/T) for hexaferrites BaCrxGaxFe12À2xO19 (x = 0.2 6.24 2.0 3.0 3. types and number of charge carriers.5 7. tan d) decreased sharply at lower frequency and slowly at higher frequency.77 0.0 500.1 3. The chances of electrons to approach the grain boundaries become very low.87 4.07 0.0 9.68 7.e.5 2.4) hexaferrites at room temperature grain boundary defects etc..44 0.4 8.5 9. The electrons follow the change in applied electric field as long as the time required for hopping is less than the alternating time period of the applied electric field and this may be the main cause for the dispersion in M-type hexaferrites. tan d) with the increasing frequency (Ref 38).2 3.0 0.4) Fig. dielectric constant (e¢). composition and sintering temperature of the materials (Ref 39).2 x=0.2 2. dielectric tangent loss ( tan d) and dielectric loss factor (e¢¢) of BaCrxGaxFe1222xO19 (x = 0.0G 1000/T (K ) Frequency (GHz) Fig.08 3.2 2.0 x=0.07 0.0-0.3 10. The observed variations are consistent with KoopÕs theory and Maxwell-Wagner bi-layer model (Ref 14). The grain boundaries formed during the sintering process because of the superficial reduction or oxidation of crystallites in the porous samples because of their direct contact with the firing atmosphere (Ref 35).0 x=0. According to this model.22 x = 0.84 4.36 3.0 4.Author's personal copy Table 1 AC electric conductivity (rAC).3 x=0.2 x=0.4 2.72 3.0M 1. DC resistivity (qRT). The displacement of charge carriers occurred in the direction of an applied electric field because of electronic exchange.0 2.1 x=0.01 0. The dispersion phenomenon can be explained on the basis of hopping of electrons between Fe2+ and Fe3+ ions. The electrons approach the grain boundaries by hopping. The reduction in dielectric constant (e¢) with the increasing frequency is a normal ferromagnetic behavior for hexaferrites.0G 1.6 0. Moreover.1 5.5 6.6 2. the dielectric structure of ferrites consists of conducting grains separated by a layer of insulating grain-boundaries.3 x=0.4 8. The dielectric losses in hexaferrites also depend on the conductivity where the materials of high conductivity exhibit high losses and vice versa (Ref 40).94 5.01 x = 0.4 7. Fe2+ fi Fe3+ + eÀ1. The dielectric tangent loss ( tan d) depends on different factors such as stoichiometry..0 9. The higher dielectric constant at lower frequencies reduces the penetration depth of electromagnetic waves by increasing the skin effect. (Ref 34). The reduction in polarization with the increasing applied field frequency is because of the reason that electronic exchange between the charge carriers cannot respond the alternating field beyond certain applied frequencies because of the smaller relaxation time and ultimately it becomes independent of it.0G 2. activation energy (Ea).5 8.0 3.16 10.0 2.0 6.0-0. drift mobility (ld).0 x=0. i.01 0.8 3.0 x=0. This disrupts the polarization buildup in the material and decreased the dielectric parameters (e¢.4 3.5 6. which in turn depends on synthesis technique.0 5.5G 2.2 x=0.1 x=0.55 9. 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). etc.30 0.49 0. 4 Frequency-dependent dielectric constant (e¢) of BaCrxGax Fe12À2xO19 (x = 0.0-0.5 7.3 3.4) hexaferrites Parameters rac 9 10À3 (X cm)À1 at 500 MHz rac 9 10À2 (X cm)À1 at 3 GHz qRT (X cm) 9 109 at 293 K ld (cm2/V s) 9 10À13 at 293 K e¢ at 3 GHz Tand at 3 GHz e¢¢ at 3 GHz x = 0. which is responsible for the polarization. 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¢.36 1.5 8. Journal of Materials Engineering and Performance .0 -1 'ρ' Log x=0.5 3. The hexaferrite materials are anisotropic and have a higher value of intrinsic magnetocrystalline anisotropy field as compared with the spinel ferrites and garnets.5 4.26 0. If the resistance of a grain boundary is high. which offer opposition to the conduction process.72 4. tan d) with the increasing frequency because of very fast variations of the applied fluctuating electric field.0 Dielectric constant (ε´) (ohm-cm) x=0.

4 0.10 0. 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. The polarization response increasingly lagging-behind the applied electric field as the frequency of applied field reaches the relaxation 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). 6 Frequency-dependent (1 MHz-3 GHz) dielectric loss factor (e¢¢) for BaCrxGaxFe12À2xO19 (x = 0.5G 2.22 0. 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.04 0. This power loss may be very much significant at applied electric field frequencies nearer to the vicinity of relaxation frequencies for each dipole for a particular dielectric material (Ref 42).1 0.5 High-Frequency Dependence of Electric Modulus.Author's personal copy 0.5G 2.00 -0.02 0. applied field frequency at room temperature the peaks shift toward lower frequency region with the increasing Cr-Ga contents. The decrease in dielectric constant and increase in loss tangent with the increasing Cr-Ga contents is suitable for high-frequency applications.18 0.02 0.1 x = 0.4 x=0. 3.24 0. while the values of dielectric loss tangent tan d (e) and loss factor (e¢¢) increased with the increasing Cr-Ga contents.02 0.2. which reduced with increasing the applied field frequency.0 500. 22) that the Cr and Ga ions preferentially occupy the octahedral sites.2.02 x=0.2.16 0.0M 1.0G 2.0 x = 0. The dielectric constant values of all samples continuously decreased. 5 Frequency-dependent (1 MHz-3 GHz) dielectric tangent loss ( tan d) of BaCrxGaxFe12À2xO19 (x = 0. 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 factor was calculated using the relation e00 ¼ e0 tan d (Ref 41).2.4) at room temperature as a function of applied field frequency in the range of 1 MHz-3 GHz.3 x=0.08 0. e¢¢ and tan d). 3. loss tangent ( tan d) and loss factor (e¢¢) at a particular frequency of 3 GHz.0-0. The shifting of the resonance peaks toward lower frequencies region shows a decrease of the resonance frequency.3 x = 0.5G 3.14 0.0G 2.22 0.10 0. The internal friction hindered the movement of each dipole.4) hexaferrites vs.0-0. interpret and analyze the electric transport mechanism in the hexaferrite materials.1 x = 0.08 0. Figure 7 inset shows that some peaks are also appeared in the profile of Z¢¢ versus frequency.1 x=0.12 0.16 0. Therefore.2 x=0. Moreover. The higher frequency Z¢¢ peak may indicate the range of frequencies in which the ions are confined to their potential wells and can make localized motion within the well (Ref 45).0 x=0. It is already reported (Ref 21.2 x = 0.04 0.4 High-Frequency Dependence of Impedance.4 0.20 Dielectric tangent loss (Tanδ) Dielectric loss factor (ε'') 0.0G Frequency (GHz) Frequency (GHz) Fig. The dissipation factor directly depends on the value of loss tangent ( tan d). It is observed that the value of M¢ is smaller in the lower frequency region.2 High-Frequency Dependence of Dielectric Loss Factor (e¢¢).14 0. which leads to heating in the sample and power loss.0-0. The conduction mechanism in these ferrites is based on the hopping of electrons between ferric (Fe3+) and ferrous (Fe2+) ions at the octahedral sites.0 3.0 x = 0. and hence the hopping of electrons between Fe2+ and Fe3+ ions also decreased. these nanomaterials may be used as high-frequency absorber (Ref 7-9).20 x=0. Figure 6 shows the profile of dielectric loss factor (e¢¢) at room temperature as a function of applied field frequency in the range of 1 MHz-3 GHz.06 0.2 x=0.06 0. 3. The complex electric modulus is a very significant tool to determine.0G 1. Table 1 shows the composition dependence of dielectric constant (e¢). The complex parts of impedance (Z¢¢) almost became independent from frequency for higher frequencies region (Ref 44). 3.3 x = 0.0G 0.4 x=0.5G x=0. the position of the peaks shifted toward the lower frequencies region with the increasing Cr-Ga contents.0G 1.0M 1. 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 field frequency. The dielectric loss is an essential part of the total core loss in hexaferrites. The real part of the complex modulus (M¢) was calculated using the relation (Ref 4).12 0. 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.3 x = 0.00 -0.4) hexaferrites at room temperature Fig.0 500. Figure 7 shows the real (Z¢) and complex (Z¢¢ inset) impedance of the hexaferrites BaCrxGaxFe12À2xO19 (x = 0. 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 influence Journal of Materials Engineering and Performance .2 x = 0.24 x = 0. Figure 8 shows the variation of real part of modulus (M¢) at room temperature as a function of applied field frequency in the range of 1 MHz-3 GHz.18 0.3 Composition Dependence of Dielectric Parameters (e¢.

0G Frequency (GHz) Frequency (GHz) Fig.38 0. The microwave absorbing materials are coated on the metallic structures to reduce the scattering.46 0. The reflection loss is measured at the optimum values of the matching thickness (tm) determined earlier (Ref 49) which is expressed by the following equation: Journal of Materials Engineering and Performance . This type of trend favors the conduction phenomena and may be because of long-range mobility of charge carriers (Ref 46).010 0.36 0.0M 1.2 0.1 60 x=0.0).4 70 x=0. the reflection coefficient RL (dB) of electromagnetic wave. the impedance match between the material and free space is required.1 x = 0.3 x = 0. the loss is the conversion of electromagnetic wave energy into heat.0 x = 0.025 0. The permeability l¢ should increase and e¢ should decrease to satisfy the impedance match.3)..1 Real part of impedance 'Z' (ohm) x=0.0 500.0G 1.4 0.0G Frequency (GHz) 2. and t is the thickness of samples. The values of M¢¢ were also higher in the lower frequency region and decreased with the increasing frequency.4 0.12 0. 0.22 0.2.1 x = 0.0G 2. 8 Frequency-dependent complex modulus (M¢) and (M¢¢ inset) of BaCrxGaxFe12À2xO19 (x = 0. 0. the permeability l¢ is very much smaller than e¢ at microwave frequency for most of the electromagnetic materials.0 50 40 30 20 10 0 1.0. under perpendicular wave incidence at the surface of a single-layer material backed by a perfect conductor can be defined by the equation (Ref 47): RL ðdBÞ ¼ À20 log10 Zin À Z0 Zin þ Z0 ! ðEq 14Þ where Z0 = 377 X.26 0.0 x=0. Therefore.0G x=0.0G 2.6G 2. small permittivity e¢.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=0.020 0.2 x=0.2 x = 0.1 x = 0.34 0.4 x=0.0G 1. The microwave absorbing materials are characterized by the permittivity (e = e¢ À je¢¢) and permeability (l = l¢ À jl¢¢). where l and e are the complex permeability and permittivity of the absorbing mate- rial.2.8G x = 0. for the absorber medium.0 500.055 0.0G Frequency (GHz) x=0.1 x=0.30 0. the electromagnetic materials with excellent absorbing ability should have high permeability l¢.4 x=0.0-0.3 x=0.48 0. The imaginary parts such as e¢¢ and l¢¢ account for the microwave energy loss in the materials. Second.4) hexaferrites at room temperature Fig.070 0.3 Microwave Absorption Properties Figure 9 shows the variation of magnetic loss tangent tan dðlÞ of M-type hexaferrites BaCrxGaxFe12À2xO19 (x = 0.015 -0.4 x=0.020 0. It is observed that the magnetic loss tangent tan dðlÞ enhanced with the increasing frequency for all the samples (x = 0.015 0.0 500.2 x = 0.2 x = 0.44 0.32 0.4 x=0.065 0.20 0.42 0.3 x = 0. le = 1. respectively.3) is higher than that of the unsubstituted one (x = 0. i.40 0. the normalized input impedance (Zin) at the air-absorber interface is represented by (Ref 48) !  rffiffiffiffiffiffiffiffiffiffiffiffiffiffi  lr 2pft pffiffiffiffiffiffiffiffi tanh Àj ðEq 16Þ lr er Zin ¼ Z0 c er where lr = l¢ À jl¢¢ and er = e¢ À je¢¢ complex permeability and complex permittivity respectively.1 x = 0.3 x = 0.14 0. 7 Frequency-dependent real (Z¢) and complex (Z¢¢ inset) impedance of BaCrxGaxFe12À2xO19 (x = 0.045 0. and large magnetic or dielectric loss at microwave frequency.0G 2. It also shows the variation of magnetic loss tangent tan dðlÞ with the increasing Cr-Ga contents. According to transmission line theory.040 0.5G 2.0-0.035 0. 9.0 x = 0.10 x=0. 3.8G 3.3) at room temperature as a function of applied field frequency in the range of 1 MHz-3 GHz .2 x = 0. The magnetic loss tangent tan dðlÞ continuously increased with the increasing Cr-Ga concentration as shown in Fig. The imaginary part of complex modulus (M¢¢) was calculated using the relation (Ref 5).005 -0.2 Imaginary part of complex modulus 0.5G 2.2G 2.16 0.5G 3.0G 2. Usually.0M 1.0 x = 0. Figure 8 inset shows the variation of imaginary part (M¢¢) of the complex modulus versus applied field frequency at room temperature.5G 2. 0.0 x=0.3 x = 0.1 x = 0.2.0M 1.010 -0. There are two necessary requirements for low reflection.4 x=0.28 0. f is the frequency. The first requirement is that the reflection of incident electromagnetic waves penetrating into the material should be lowest.5G 3.Author's personal copy 80 Complex impedance Z" (ohm) x=0.3 x = 0.000 -0. c is the velocity of light. In fact.0G 1.3 x=0. 0. The observed behavior of the complex modulus (M¢¢) is because of the same reasons as mentioned for the variation of dielectric loss factor (e¢¢).4) hexaferrites at room temperature of induced electric field. the characteristic impedance of free space and is given by Z0 ¼ rffiffiffiffiffi l0 : e0 ðEq 15Þ For a microwave absorbing layer terminated by a short circuit.005 0.18 0. the synthesized material should have higher imaginary part of permittivity e¢¢ or permeability l¢¢ at microwave frequency to effectively absorb the incident electromagnetic wave.5G 3.060 0.030 0.24 0. The conditions for impedance matching at which Zin becomes equal to Z0 are satisfied at particular matching thickness (tm) and matching frequency (fm). 0. In order to fulfill the first requirement.3 x=0.050 0. The magnetic loss tangent tan dðlÞ for the substituted samples (x = 0.3 x = 0.e.0. The second requirement is that the material should absorb the maximum amount of electromagnetic waves.4G 2.0 x = 0.

in the present study.3) hexaferrites at room temperature 4.2. Technol.M.02 -0. S. The appearance of such absorption peaks for the substituted samples (x = 0.02 0. and I.00 0.0G 1. L. 0. f is the incident frequency of free space.04 0. The wide absorption bandwidths and low reflection loss peaks make the materials useful for microwave applications.2 x=0.08 Ga=0. 9 Frequency-dependent (1 MHz-3 GHz) magnetic loss tangent tan dðlÞ for BaCrxGaxFe12À2xO19 (x = 0.5G 3. Figure 10 shows high-frequency 1 MHz-3 GHz-dependent reflection coefficient (C) for the M-type BaCrxGaxFe12À2xO19 (x = 0. H.. The synthesized M-type hexaferrite materials are excellent materials for high-frequency applications. H. X. S. Katynkina. and low matching thickness.88 Magnetic loss tangent 0. G. AC conductivity (rAC) enhances with the increase of the applied field frequency.3) hexaferrites at room temperature. the synthesized materials can be considered as potential candidates for high-frequency applications such as microwave radiations absorption. and X. K.0.0G 0.0 500.5 GHz x=0.06 1.08 0. Horikawa.3 x=0. camouflaging. camouflaging. where ka is the wavelength inside the absorber. The absorption peak appeared for the unsubstituted sample (x = 0. References 1.92 0.2. A good microwave absorption material needs to have low reflection loss.0M 1. Conclusions tm ¼ ka c ¼ pffiffiffiffiffiffiffiffi 4f lr er 4 ðEq 17Þ An economic and simple technique sol-gel autocombustion has been used to synthesize the Cr-Ga-substituted BaM hexaferrites. large magnetic or dielectric loss. Machida.0 1. and K.94 0.0G 1. 0. Hu.3 0.96 0.0) at a particular frequency of 2.5 GHz as shown in Fig.. The temperature-dependent DC resistivity exhibits the semiconducting nature. and reduction of dielectric constant and reflection loss at microwave frequency.0 Ga=0. Zhou. G. DC resistivity improves.M. A. p 1391–1395 3.86 -0. X. Letyuk.0G 0.G. Ryabov.14 1.02 1. 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 field (Ref 16. J.2 x=0.2. 0. The Regularity of Microstructure Formation and Its Influence on the Journal of Materials Engineering and Performance . However.90 0. The similar trend was also observed earlier in the case of M-type barium hexaferrites (Ref 49). Compos.3) are also expected in the frequency range greater than 3 GHz. T.0 x=0. 17). Mater. Masuda.0. Li. because the shifting of peaks occurs with the increasing Cr-Ga contents. 10 Frequency-dependent (1 MHz-3 GHz) reflection coefficient (C) for BaCrxGaxFe12À2xO19 (x = 0. and attenuations of electromagnetic interference.0G 2.04 0. and attenuations of electromagnetic interference because of their enhanced electric resistivity. 0.3 1.3 x=0. while drift mobility drops with the increase of Cr-Ga contents. Miura. Attractive Microwave-Absorbing Properties of La1ÀxSrxMnO3 Manganite Powders. Chem. The dielectric constant and tangent loss tan dðeÞ decrease with the increase of applied field frequency in the range of 1 MHz-3 GHz.0G 2. Microwave Absorption Properties of the Nano-Composite Powders Recovered from Nd-Fe-B Bonded Magnet Scraps. the reflection coefficient decreased with the increasing applied field frequency as well as with the increasing Cr-Ga contents. Hence. p 2003 4. 0.2 Ga=0.0 2. The maximum value of the DC resistivity is observed for the sample (x = 0. 10.5G 2. Gorelik. Alloys Compd. Fan.G. 408–412. The samples substituted with Cr-Ga contents have lower values of dielectric constant and higher values of loss tangent compared with the unsubstituted sample.18 0. M. 2006.D.0-0. such as microwave radiations absorption. 75(1–3).2 Reflection coefficient x=0.J.5G 2.0M 1.10 0. The magnetic loss tangent tan dðlÞ continuously improves with the increase of applied field frequency as well as with the increase of Cr-Ga contents. Li. The reflection coefficient (C) is also reduced with the increase of Cr-Ga contents.0 500.98 0. There exists no ideal material which fulfills all these requirements. Gonchar.04 x=0. 2006. M. Liu. Magnetic and Microwave Absorbing Properties of Core-Shell Structured MnFe2O4/ TiO2 Nanocomposites.16 0. and S. Synthesis. Xiao. p 101–104 2.12 0.84 Frequency (GHz) Frequency (GHz) Fig. Sci. Itoh. It is observed that the reflection coefficient (C) is decreased with the increase of applied field frequency.06 0. the wave reflected at the air-absorber interface is out of phase with the wave reflected at absorber-metal interface hence satisfying the quarter-wave thickness criteria. wide absorption bandwidth. Phys.20 0.Author's personal copy 0.4) hexaferrites at room temperature Fig.5G 3. Fu.Y..3). 2002. 66. This equation shows that when the thickness of absorber is equal to one quarter of wavelength.00 x=0.

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