ISSN 1061 3862, International Journal of Self Propagating High Temperature Synthesis, 2013, Vol. 22, No. 2, pp.

9398. Allerton Press, Inc., 2013.

Combustion Synthesized Ferrites and Ferroelectrics for Microwave Applications

M. B. Shelar and V. Puri
Thick and Thin Film Device Lab., Department of Physics, Shivaji University, Kolhapur, Maharashtra, 416004 India e mail: mahesh6684@yahoo.co.in
Received December 13, 2012

AbstractThe individual phases of Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6) ferrite and Ba0.8Sr0.2TiO3 ferroelectric (BST phase) were successfully prepared by autocombustion route. The oscillatory behavior of transmittance for the NiCd ferrite was observed at about 0.44 at 8.2 GHz. The absorption study depicts the hopping phe nomena of microwaves through the NiCd phase. The dependence of microwave conductivity on ferrite con tent was discussed. The dielectric permittivity of NiCd ferrites varied between 10 and 30. Compared to the NiCd phase, the transmittance of the Ba0.8Sr0.2TiO3 phase was found to be low. The dip in reflection loss for Ba0.8Sr0.2TiO3 is equivalent to the minimum reflection or the maximum absorption of the microwave power for BST phase. The maximum microwave conductivity for Ba0.8Sr0.2TiO3 was found to be about 0.459 S/cm. The high microwave permittivity for Ba0.8Sr0.2TiO3 had a value of about 120.21. Keywords: combustion synthesis, ferrite, ferroelectric, microwave properties DOI: 10.3103/S1061386213020088

INTRODUCTION Many of magnetic microwave devices have been devised with dielectric and magnetic substrates [1]. Many techniques have been developed to measure the permittivity. The complex permittivity is an important factor which can be altered to achieve maximum absorption of electromagnetic waves [24]. The microwave electromagnetic properties of the magne sium substituted zinc manganese ferrites have been studied for the frequency range from 2 to 18 GHz [5]. It was shown that the values of ' and '' decreased slightly with substitution of magnesium. The micro wave absorption can be attributed to both dielectric loss and magnetic loss from the loss tangents of the sample [6]. The complex permittivity, complex permeability, and microwave absorption properties of the BaCe0.05Fe11.95O19 powder were measured by the transmission/reflection coaxial line method in the range of 813 GHz [7]. The results show that the resulting powder has a minimum reflection loss value of 37.4 dB at 12.8 GHz with a matching thickness of 3.5 mm. The microwave sintering treated barium fer rite materials possess excellent properties with a satu ration magnetization of 53.6 emu/g and coercive force of 623.8 Oe [8]. Also, in the frequency range 1 MHz 1.8 GHz, the real and imaginary part of permeability is between 1.83.0 and 00.55, and the real and imag inary part of dielectric constant is between 2.42.7 and 00.15, respectively.
93

In this work, we combustion synthesized the Ni1 xCdxFe2O4 ferrite and Ba0.8Sr0.2TiO3 ferroelectric for use in microwave tunable devices and high charge density capacitors. EXPERIMENTAL High purity AR grade Ni(NO3)2 6H2O, Cd(NO3)2 4H2O, and Fe(NO3) 9H2O were used to prepare Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6). The raw material was heated at 80C to evolve NO2, CO2, and H2O. The10% PVA (polyvinyl alcohol) and sucrose were added to nitrates solution. The sucrose acted as a fuel for the combustion purpose while PVA was used to form polymer regions with trapped metal ions. The dried and fluffy gel gets burnt in a self propagating manner at about 200C. The obtained ash was then calcined at 600C for 6 h. The same procedure was fol lowed to make Ba0.8Sr0.2TiO3 by using Ba(NO3)2, Sr(NO3)2 and Ti(NO3)2 as a precursor. In this case, the prepared ash was calcined at 900C for 10 h. Sucrose provides wrapping through coordination for the cations in solution and circumvents their selec tive precipitation during the evaporation process. Sucrose is always taken in excess amounts to metal ions and acts as a chelating agent. Moreover, it also serves as a fuel for the combustion reaction, being oxi dized by the nitrate ions. The chemical bonding of the cations formed on the polymeric chain in viscous solu tion. Even as the chemical bonding is destroyed during

94 1.0 0.8 T, rel. units 0.6 0.4 0.2

SHELAR, PURI x = 0.2 R, rel. units 1.0 0.8 0.6 0.4 0.2 0 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz 1.0 0.8 R, rel. units 0.6 0.4 0.2 0 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz 1.0 0.8 R, rel. units 0.6 0.4 0.2 0 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz x = 0.6 x = 0.4 x = 0.2

0 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz 1.0 0.8 T, rel. units 0.6 0.4 0.2 0 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz 1.0 0.8 T, rel. units 0.6 0.4 0.2 0 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz x = 0.6 x = 0.4

Fig. 1. Microwave transmittance (T) and reflectance (R) spectra of Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6).

the pyrolysis, the high viscosity hampered cation mobility and thus affected the crystallite morphology. In the presence of dilute nitric acid, sucrose gets hydrolyzed to fructose and glucose which further oxi dized to gluconic acid:

During pyrolysis, branched chain polymer releases gaseous products which make the resultant material highly porous and fluffy. Microwave absorption was studied in the X band (812 GHz) using the waveguide reflectometer setup [9]. The microwave permittivity was measured by using Voltage Standing Wave Ratio (VSWR) slotted section method. Real and imaginary parts of dielectric constant were calculated using the Clapham equation [10]: A 0 ' 0 ' = 1 + , " = , 360d 8.686 d
2

C12H 22O11 + [H] + H 2O C 6H12O 6(glucose) + C 6H12O 6(fructose), C 6H12O 6 + [O] C 6H12O 7(gluconic acid).
It has been found that sucrose in the presence of PVA (10%) give rise to formation of crushable and fluffy powder mixture of oxides. Also it provides for mation of a branched chain polymer network within which the metal ions are held in hydroxy pockets.

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COMBUSTION SYNTHESIZED FERRITES AND FERROELECTRICS 1.0 0.8 A, rel. units A, rel. units 0.6 0.4 0.2 0 8.0 8.5 1.0 0.8 A, rel. units 0.6 0.4 0.2 0 8.0 8.5 9.0 10.0 11.0 12.0 9.5 10.5 11.5 f, GHz x = 0.6 x = 0.2 1.0 0.8 0.6 0.4 0.2 0 8.0 8.5 x = 0.4

95

9.0

10.0 11.0 12.0 9.5 10.5 11.5 f, GHz

9.0

10.0 11.0 12.0 9.5 10.5 11.5 f, GHz

Fig. 2. Microwave absorption spectra of Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6).

where is the phase angle (deg), 0 guided wave length, d film thickness, and A attenuation difference (dB). RESULTS AND DISCUSSION Figure 1 shows the microwave transmittance and reflectance spectra for Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6) ferrites. The transmittance decreases with increasing frequency and showing an oscillatory behavior. The highest value of transmittance was about 0.44 at 8.2 GHz. The microwave absorbance for Ni1 xCdxFe2O4 is shown in Fig. 2. The increase in absorption due to an increase in the Cd content can be associated with an increase in the size of grain boundary, which creates discontinuity for microwave propagation. At higher frequencies, the increasing content of cadmium decreases hopping phenomena. The maximum value for absorption, about 0.83, is observed at 11.4 GHz. The microwave conductivity for Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6) is given in Fig. 3. As The Cd content increases, the pores in the ferrite grow in size, which leads to an increase in the size of grain boundaries,

thus putting obstacles to propagation of microwaves. The microwave conductivity decreases from 0.3 to 0.09 S/cm and its lowest value is observed for Ni0.4Cd0.6Fe2O4. The addition of Cd2+ ions leads to increasing amount of Fe3+ ions at the octahedral site, which decreases the activation energy of conduction. Hence, the mobility of ferrites decreases and this must result in lowering the microwave conductivity. The conductivity also sharply decreases with increasing frequency. The lower value of conductivity may be acceptable for use in tunable microwave devices. The real (') and imaginary ('') parts of complex permittivity in the range 812 GHz is shown in Fig. 4. The permittivity is seen to decrease with increasing frequency. The presence of Fe2+ ion in the bulk of fer rites maintains charge neutrality. The spectra of all samples show good dispersion relation between them and decreasing trend with increasing frequency. The maximum values of dielectric permittivity for all the samples varied between 10 and 30. The dielectric loss ('') is lower than that reported for bulk ferrites. The low loss values suggest that the ferrites can be suitable for high frequency applica
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INTERNATIONAL JOURNAL OF SELF PROPAGATING HIGH TEMPERATURE SYNTHESIS

96 0.30 0.25 , S/cm

SHELAR, PURI x = 0.2 0.16 0.14 0.12 0.10 0.08 0.06 0.04 0.02 0 8.0 8.5 x = 0.4

0.15 0.10 0.05 0 8.0 8.5 9.0 12.0 10.0 11.0 9.5 10.5 11.5 f, GHz 0.10 0.09 0.08 0.07 0.06 0.05 0.04 0.03 0.02 0.01 0 8.0 8.5

, S/cm

0.20

9.0

12.0 10.0 11.0 9.5 10.5 11.5 f, GHz

x = 0.6

, S/cm

9.0

12.0 10.0 11.0 9.5 10.5 11.5 f, GHz

Fig. 3. Microwave conductivity spectra of Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6).

tions. It is evident that both ' and '' values increase with increasing amount of Cd ions. In the present fer rites, the small grains are separated by a highly resistive grain boundary, which creates heterogeneity and gives rise to interfacial polarization. The microwave transmission and reflectance spec tra of Ba0.8Sr0.2TiO3 are shown in Fig. 5. For lower f, the dispersion like peaks are observed. This dispersion could be due to the presence of barrier or grain bound aries. It is clear that, at higher f, the barrier capaci tance dominates, and hence we come to lower values of transmittance. Compared to the ferrite, the trans mittance is low. The dip in reflection loss is equivalent to the minimum reflection or the maximum value of absorption of the microwave power for the BST phase. The ferroelectric phase also shows high absorption in the 812 GHz range as is seen in Fig. 6. At 9.5 GHz the absorbance attains a saturation value (0.74) which is useful for tuning the microwaves. Figure 7 shows the microwave conductivity of Ba0.8Sr0.2TiO3. The maximum value observed was about 0.459 S/cm. Due to a high dielectric constant, the BST phase is a well known material for phase shift applications. In our case, a high dielectric constant reduces the microwave conductivity of the BST phase.

Figure 8 shows the real and complex part of dielec tric permittivity for the Ba0.8Sr0.2TiO3 phase. The real part of permittivity varies between 51 and 121. At 9.5 GHz the maximum permittivity was found to be 120.21. After 9.5 GHz the reduction A decrease in permittivity above 9.5 GHz is due to residual stresses in the bulk material. Due to high permittivity, bulk Ba0.8Sr0.2TiO3 ceramics have long been used to make high charge density capacitors. CONCLUSIONS The microwave transmittance of combustion syn thesized nickel cadmium ferrites Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6) was found to attain a maximum value of around 0.4, irrespective of x. The absorbance of the ferrites increases with increasing x due to a growth in the size of pores and grain boundaries. The lowest microwave conductivity of Ni0.4Cd0.6Fe2O4 was found to be about 0.09 S/cm. The microwave dielectric per mittivity for nickel cadmium ferrites varied between 10 and 30 while the imaginary part, between 0.2 and 0.31. For the Ba0.8Sr0.2TiO3 ferroelectric (BST phase), the lowest transmittance and reflectanceabout 0.065 and 0.2 respectivelyis observed at 9.5 GHz.
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INTERNATIONAL JOURNAL OF SELF PROPAGATING HIGH TEMPERATURE SYNTHESIS

COMBUSTION SYNTHESIZED FERRITES AND FERROELECTRICS ' 30 25 20 15 0.10 10 5 0 8.5 ' x = 0.4 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz 0.05 0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz '' 0.7 x = 0.4 0.6 0.5 0.4 0.3 0.2 0.1 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz x = 0.6 0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz '' 0.35 x = 0.6 0.30 0.25 0.20 0.15 10 5 0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz 0.10 0.05 0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz x = 0.2 '' 0.25 0.20 0.15

97

x = 0.2

30 25 20 15 10 5

0 8.5 30 25 20 15 '

Fig. 4. Real and imaginary parts of permittivity for Ni1 xCdxFe2O4 (x = 0.2, 0.4, 0.6).

0.07 0.06 R, rel. units T, rel. units 0.05 0.04 0.03 0.02 0.01 0 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz

0.40 0.35 0.30 0.25 0.20 0.15 0.10 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz

Fig. 5. Microwave transmittance and reflectance spectra of Ba0.8Sr0.2TiO3. INTERNATIONAL JOURNAL OF SELF PROPAGATING HIGH TEMPERATURE SYNTHESIS Vol. 22 No. 2 2013

98 0.80 0.75 A, rel. units 0.70

SHELAR, PURI 0.50 0.45 0.40 0.35 0.30 0.25 0.20 0.15 0.10 0.05 0 8.5

0.60 0.55 0.50 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz

, S/cm

0.65

9.0

9.5

10.0 10.5 f, GHz

11.0

11.5

12.0

Fig. 6. Microwave absorbance of Ba0.8Sr0.2TiO3.

Fig. 7. Microwave conductivity spectra of Ba0.8Sr0.2TiO3.

' 140 120 100 80 60 40 20 0 8.5

9.0

'' 1.0 0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 8.5 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz

9.0 9.5 10.0 10.5 11.0 11.5 12.0 f, GHz

Fig. 8. Real and imaginary parts of dielectric permittivity for Ba0.8Sr0.2TiO3.

The real part of permittivity varies between 51 and 121. At 9.5 GHz, the maximum permittivity is found to be 120.21 while the microwave conductivity, 0.459. The BST phase exhibited the ability to change dielectric constant and dielectric loss tangent near the ferroelec tric Curie temperature which makes this material suit able for use in electrically tunable microwave devices. REFERENCES
1. Oates, D.E. and Dionne, G.F., Tunable YBCO resona tors on YIG substrates, IEEE Trans. Appl. Supercon duct., 1997, vol. 7, no. 2, pp. 23382342. 2. Chou, Y. H., Jeng, M. J., Lee, Y. H., and Jan, Y. G., Measurement of RF PCB dielectric properties and losses, Prog. Electromagn. Res. Lett., 2008, vol. 4, pp. 139148. 3. He, X., Tang, Z. X., Zhang, B., and Wu, Y., A new Deembedding Method in permittivity measurement of ferroelectric thin film materials, Prog. Electromagn. Res. Lett., 2008, vol. 3, no. 1, pp. 18. 4. Jadhav, R.N. and Puri, V., Microwave absorption, conductivity, and complex permittivity of fritless Ni1 xCuxMn2O4 (0 x 1) ceramic thick film: effect of

5.

6.

7.

8.

9.

10.

copper, Prog. Electromagn. Res. C, 2009, vol. 8, pp. 149160. Songa, J., Wanga, L., Xua, N., and Zhanga, Q., Micro wave absorbing properties of magnesium substituted MnZn ferrites prepared by citrateEDTA complexing method, J. Mater. Sci. Technol., 2010, vol. 26, no. 9, pp. 787792. Zhou, K., Deng, J., Yin, L., Ma, S., and Gao, S.H., Microwave absorbing properties of La0.8Ba0.2MnO3 nanoparticles, Trans. Nonferr. Met. Soc. China, 2007, vol. 17, no. 5, pp. 947950. Changa S., Kangninga S., and Pengfeia C., Microwave absorption properties of Ce substituted M type barium ferrite, J. Magn. Magn. Mater., 2012, vol. 324, no. 5, pp. 802805. Yang Q., Zhang, H., Liu, Y., and Wen, Q., Microstruc ture and magnetic properties of microwave sintered M type barium ferrite for application in LTCC devices, Mater. Lett., 2009, vol. 63, nos. 34, pp. 406408. Vhankhande, B. B., Jadhav, S.V., Kulkarni, D.C., and Puri, V., Investigations on the microwave properties of electropolymerized polyaniline thin films, Microwave Opt. Technol. Lett., 2008, vol. 50, no. 3, pp. 761766. Kulkarni, D.C. and Puri, V., Ku band microwave stud ies of fritless strontium hexaferrite thick films, Micro electron. Int., 2010, vol. 27, no. 3, pp. 143147.
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