ARTICLE IN PRESS

Journal of Magnetism and Magnetic Materials 279 (2004) 195201

Structural and magnetic properties of NiZn ferrites prepared by microwave sintering

Monica Sorescua,*, L. Diamandescua, R. Peelamedub, R. Royb, P. Yadojic
a

Physics Department, Bayer School of Natural and Environmental Sciences, Duquesne University, 211 Bayer Center, Pittsburgh, PA 15282-0321, USA b Pennsylvania State University, 102 Materials Research Laboratory, University Park, PA 16802-4801, USA c Center for Materials for Electronic Technology (C-MET), Cherlapally, HCL (PO), Hyderabad 500 051, India Received 5 June 2003; received in revised form 6 January 2004

Abstract A series of ferrites was prepared using microwave sintering, starting with both hematite and magnetite precursors in the Ni1xZnxFe2O4 (x=01) system. X-ray diffraction measurements were performed to yield the lattice constant as function of the amount x of Zn substitution. For both hematite and magnetite series, the lattice parameter was found to . increase with increasing x. Mossbauer spectroscopy was performed at room temperature and spectra were analyzed using the binomial distribution. The hyperne magnetic eld of the octahedral sublattice was found to decrease with increasing the number of Zn nearest neighbors for all values of the substitution level. The area of the tetrahedral sublattice decreases with increasing x and the sublattice area of the octahedral sites increases correspondingly for both series of samples, as a result of substitution of iron by zinc in the tetrahedral sites. The hyperne magnetic eld of the tetrahedral sublattice was found to decrease as function of Zn amount x, for both hematite and magnetite series. However, in most cases, the hyperne magnetic elds for the magnetite series are slightly less than those corresponding to the hematite series. r 2004 Elsevier B.V. All rights reserved.
PACS: 76.80 . Keywords: Magnetic materials; Ferrites; Substitutions; Mossbauer spectroscopy; X-ray diffraction

1. Introduction Ferrites crystallize in a spinel structure, in which both divalent and trivalent cations are distributed among tetrahedral (A) and octahedral (B) sites. The site preference exhibited by divalent ions
*Corresponding author. Tel.: +1-412-396-4166; fax: +1412-396-4829. E-mail address: sorescu@duq.edu (M. Sorescu).

denes whether the spinel is normal, inverse or mixed. In most cases, magnetic divalent cations (such as Ni2+) prefer the octahedral sites and produce an inverse spinel structure. Diamagnetic divalent cations (such as Zn2+) have preference for the tetrahedral positions and the resulting structure is a normal spinel. Due to their various technological applications, NiZn ferrites have attracted recently considerable research interest. The ferrites, in powder or thin

0304-8853/$ - see front matter r 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2004.01.079

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196 M. Sorescu et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 195201

lm forms, were prepared by the high-temperature solid-state reaction method [1], coprecipitation [2], solgel method [3], pulsed laser deposition [4], high-energy ball milling [5] and hydrothermal technique [6]. However, the relationship between microstructure and magnetic properties of this system is not yet understood. The fundamental difference in the heating mechanism of microwave sintering offers unique advantages over conventional sintering processes. In conventional heating, the heat is generated by heating elements (in resistive heating) and then transferred to sample via radiation, conduction and convection, which requires a long duration for sintering the materials that causes some of the constituents to evaporate, thereby modifying the desired stoichiometry and allow undesired grain growth. In microwave heating, the materials absorb microwave energy themselves and then transform it into heat within the sample volume and sintering can be completed in shorter times. Major advantages of microwave processing are higher efciency, enhanced reaction and sintering rate as well as shorter cycle times and cost savings. In this paper we propose the synthesis of the NiZn ferrite system using the microwave technique and attempt to characterize the structural and magnetic properties of the ferrite samples using . XRD and Mossbauer spectroscopy. In particular, this approach is expected to conrm or rule out the possible occurrence of Fe2+ ions in these systems, which could eventually explain the different dielectric behavior observed for samples with magnetite or hematite precursors [7].

NiZn ferrites are very good microwave absorbers, preliminary experiments showed that the thermal runaway has caused stress-induced cracks throughout the sample. In order to prevent this problem, the samples were placed on a thin SiC plate that also acted as a pre-heater. In our experiments, the emissivity of the single wavelength IR pyrometer was set at e=0.75, and this value was chosen by calibrating against the optical pyrometer set at the other side of the tube [7]. The X-ray diffraction (XRD) spectra were recorded with a Rigaku D-2013 diffractometer with CuKa ( The Mossbauer . radiation (l=1.540598 A). spectra were recorded at room temperature using a source of 57Co in Rh matrix and an MS-1200 constant acceleration spectrometer. All spectra were analyzed by nonlinear least-squares tting using the NORMOS program.

3. Results and discussion Fig. 1 plots the lattice constant as function of the amount x of Zn substitution, for both hematite and magnetite precursors, derived from the XRD spectra. It can be observed that in both cases, the lattice parameter increases linearly with increasing x, due to the greater ionic radius of zinc ions ( with respect to the ionic radius of iron (B0.74 A) ( ions (B0.55 A). Fig. 2(a)(f) shows the room temperature trans. mission Mossbauer spectra of the Ni1xZnxFe2O4
8.46 8.44

Lattice constant ()

2. Experimental Ni1xZnxFe2O4 (x=01) were prepared using high-purity NiO, ZnO, Fe3O4/Fe2O3 in stoichiometric proportions. The powders after thorough mixing and grinding were calcined at 1100 C for 4 h. All compositions were sintered at 1275 C for 30 min using a multimode microwave furnace (2.45 GHz, Amana Radarange, Model RC/20 SE) operating at maximum input power of 2.0 kW (the output power of magnetron is roughly 5060% of the input power). Despite the fact that

8.42 8.40 8.38 8.36 8.34 8.32 0.0 0.2 0.4 0.6 0.8 1.0 1.2

from hematite from magnetite

Zn Content x
Fig. 1. Lattice constant as function of the level x of Zn substitution, for both hematite and magnetite series.

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M. Sorescu et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 195201
1.0 0.9

197

1.0 0.9

0.8 0.7 1.0 0.9 0.8 x= 0.8 0.7 1.00

(f)
x= 1.0

x=1.0
0.8 1.00 0.88

(f)

(e)

x=0.8
0.76 1.00
Relative transmission

(e)

0.97 0.94 1.00

Relative transmission

0.99 0.98 0.97 1.00 x= 0.6

x=0.6

(d)

(d)

0.98 x= 0.4 0.96 1.00 0.97 x= 0.2 0.94 1.00 0.96 0.92 0.88 -10 -5 0 5 10 x= 0.0

0.98
(c)

x=0.4

(c)

1.00 0.96

x=0.2
(b)

(b)

0.92 1.00 0.96 0.92

x=0.0
0.88
(a)
-10 -5 0 5

(a)
10

Velocity (mm/s)
. Fig. 3. Room temperature transmission Mossbauer spectra of the Ni1xZnxFe2O4 (x=01) system: (a) x=0, (b) x=0.2, (c) x=0.4, (d) x=0.6, (e) x=0.8 and (f) x=1 for the magnetite precursor.

Velocity (mm/s)
. Fig. 2. Room temperature transmission Mossbauer spectra of the Ni1xZnxFe2O4 (x=01) system: (a) x=0, (b) x=0.2, (c) x=0.4, (d) x=0.6, (e) x=0.8 and (f) x=1 for the hematite precursor.

(x=01) system obtained from hematite and . Fig. 3(a)(f) presents the Mossbauer spectra recorded in transmission at room temperature for the nickelzinc ferrites synthesized from a magnetite precursor. The spectra are similar, but in some cases the ones corresponding to magnetite exhibit

lower values of the hyperne magnetic elds than those observed for the hematite precursor series. This could be due to a different absorption process of microwaves in the two precursors [7]. The spectra were analyzed by least-squares tting using the binomial distribution model [8]. The rened

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Table 1 . Mossbauer t parameters of Ni1xZnxFe2O4 (from hematite) Sample Code NZ1 NZ2 x 0.0 0.2 0.262 0.393 0.246 0.082 0.187 0.311 0.276 0.138 0.138 0.276 0.311 0.186 0.047 49.1 52.5 49.4 52.6 49.2 46.5 41.5 45.5 48.7 47.2 42.7 38.7 33.2 42.5 38.4 24.3 9.1 27.9 70.2 0.22 0.29 0.33 0.27 0.23 0.24 0.24 0.27 0.28 0.23 0.29 0.33 0.34 0.30 0.26 0.37 0.33 0.20 0.3 0.25 0.38 70.01 0.07 0.08 0.11 0.11 0.3 0.11 0.41 0.08 0.11 0.04 0.11 0.005 0.09 0.02 0.04 0.02 0.04 0.33 0.40 56 44 40.2 14.8 24.1 14.9 5.9 30.1 14.2 23.8 21.2 10.5 20.9 11.5 23.5 26.4 15.8 1.7 94 6 100 70.4 NiFe2O4 A (tetra) NiFe2O4 B (octa) A B0 (n=0) B1 (n=1) B2 (n=2) B3 (n=3) A B1 B2 B3 (n=3) B4 (n=4) A B2 B3 B4 B5 (n=5) B6 (n=6) ZnFe2O4 B4,B5,B6 (hyperne magnetic eld collapse) ZnFe2O4 P(n,x) Hhf (T) ISa (mm/s) QSb (mm/s) Relative areas (%) Site assignment

NZ3

0.4

NZ4

0.6

NZ5

0.8

NZ6 Errors
a b

1.0

0.34 70.01

IS is the isomer shift and is given relative to a-Fe. QS is the quadrupole shift.

values of the hyperne parameters are given in Tables 1 and 2 for hematite and magnetite precursors, respectively. In Figs. 2 and 3(a) we represented the . Mossbauer spectrum of NiFe2O4 with x=0. This nickel ferrite is an inverse spinel and was decomposed into two sextets, corresponding to the tetrahedral and octahedral magnetic sublattices. Unlike the case of magnetite and because Ni is a magnetic ion, the hyperne magnetic eld of the octahedral sites is greater than that of the tetrahedral sites. Moreover, the isomer shift of the octahedral sites is greater than that of the tetrahedral sites. Because values greater than IS=0.5 mm/s and QS=1 mm/s are expected for Fe2+, our experiments rule out the possible occurrence of Fe2+ ions in this system. For x=0.2 in Figs. 2 and 3(b) we obtained the . best t by employing 5 sextets in the Mossbauer

spectra, one sextet A for the tetrahedral sublattice and four sextets, B0, B1, B2 and B3 representing the octahedral sites, in agreement with the values of the distribution probabilities P(n,x) of Zn substitutions in the tetrahedral sites of the NiZn ferrite lattice. The subscripts 0, 1, 2,y,n represent the number of Zn ions in tetrahedral positions around an octahedral one. The sublattices with P(n,x) lower than B4% have very small . contributions in the Mossbauer spectra and can be omitted. In Figs. 2 and 3(c) we refer to the Ni1xZnx Fe2O4 system with x=0.4 for hematite and magnetite precursors, respectively. The spectra were tted using 5 sextets, A for the tetrahedral sites and B1, B2, B3 and B4 for the octahedral positions. At this substitution level, the sextet corresponding to number n=0 of Zn nearest neighbors has close to zero probability in the

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M. Sorescu et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 195201 Table 2 . Mossbauer t parameters of Ni1xZnxFe2O4 (from magnetite) Sample Code NZF1 NZF2 X 0.0 0.2 0.262 0.393 0.246 0.082 0.187 0.311 0.276 0.138 0.138 0.276 0.311 0.186 0.047 49.4 52.7 48.7 51.5 48.4 45.8 41.8 45.7 48.8 45.6 40.7 36.3 34.4 42.2 39.0 23.7 5.4 30.6 70.2 0.20 0.29 0.32 0.30 0.20 0.24 0.26 0.34 0.25 0.15 0.39 0.29 0.32 0.35 0.31 0.25 0.36 0.16 0.36 0.08 0.08 0.11 0.09 0.23 0.11 0.39 0.015 0.07 0.23 0.11 0.18 0.05 0.19 0.12 0.18 0.06 0.34 0.44 51.5 48.5 40.7 15.0 24.1 15.1 5.0 30.1 14.2 23.8 21.2 10.5 27.6 11.8 20.0 24.8 14.9 0.8 81.5 18.5 100 70.4 NiFe2O4 A (tetra) NiFe2O4 B (octa) A B0 (n=0) B1 (n=1) B2 (n=2) B3 (n=3) A B1 B2 B3 (n=3) B4 (n=4) A B2 B3 B4 B5 (n=5) B6 (n=6) ZnFe2O4 B3, B4, B5, B6 (hyperne magnetic eld collapse) ZnFe2O4 P(n,x) Hhf (T) ISa (mm/s) QSb (mm/s) Relative areas (%) Site assignment 199

NZF3

0.4

NZF4

0.6

NZF5

0.8

NZF6 Errors
a b

1.0

0.36 70.01

0.34 70.01

IS is the isomer shift and is given relative to a-Fe. QS is the quadrupole shift.

binomial distribution and congurations with a higher number of substitution level n become probable. For x=0.6 in Figs. 2 and 3(d) the best t was obtained with 6 subspectra, namely A and B2, B3, B4, B5 and B6, with the remark that B6 becomes a doublet, due to the fact that all the iron atoms in the tetrahedral sites were substituted by Zn. . Indeed, it is known that the Mossbauer spectrum of the zinc ferrite is a doublet, but this pattern can be eventually omitted, since it contributed less than 1% to the spectral area. In Figs. 2 and 3(e) for x=0.8 we observe the appearance of the doublet associated with the Znferrite structure. For x=1 in Figs. 2 and 3(f) we reproduce the spectrum of ZnFe2O4 ferrite system, which is a direct spinel. In this lattice, diamagnetic Zn2+ ions prefer the tetrahedral positions, while Fe3+ ions occupy the octahedral sites.

Figs. 4 and 5 show the dependence of the hyperne magnetic elds Hhf extracted from the . Mossbauer spectra for hematite and magnetite precursors, respectively. The hyperne magnetic eld of the octahedral sublattice decreases with increasing the number n of Zn ions substituting iron, because few iron neighbors remain on the tetrahedral positions. Moreover, the hyperne magnetic eld of the tetrahedral sites decreases with increasing the Zn amount x, because this diamagnetic substitution occupies the tetrahedral sites and consequently, lowers the magnetic hyperne eld at these sites. Figs. 6 and 7 display the dependence of the sublattice area on the Zn concentration x for both hematite and magnetite series. The experimental lines follow closely the theoretical plots based on the chemical formula. The area of the tetrahedral sublattice decreases with increasing the amount x

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Ni1-xZnxFe2O4 (from hematite)

60 x=0.2 x=0.4 x=0.6 50
60

Ni1-xZnxFe2O4 (from magnetite)

50

x=0.2 x=0.4 x=0.6

Hyperfine magnetic field, Hocta (T)

Hyperfine magnetifc field, Hocta (T)

40

40

30
50

30

50

45

45

20

H tetra (T)

Htetra (T)

20

40

40

35

35

10
30 0.0 0.2 0.4 0.6 0.8

10
30 0.0 0.2 0.4 0.6 0.8

0 0 1 2 3 4 5 6

n
Fig. 4. Dependence of the hyperne magnetic elds on the number n of Zn neighbors for the NiZn ferrite obtained from hematite precursor.

Fig. 5. Dependence of the hyperne magnetic elds on the number n of Zn neighbors for the NiZn ferrite obtained from magnetite precursor.

of Zn content, which substitutes Fe at the tetrahedral sites. Similarly, the area of the octahedral sublattice increases with x, because more Fe will be found at the octahedral positions, while Zn occupies the tetrahedral sites.
Sublattice area (%)

Ni1-xZnxFe2O4 ( from hematite )

100

80
tetrahedral

4. Conclusions The system Ni1xZnxFe2O4 (x=01) was synthesized from both hematite and magnetite precursors using the microwave technique. The samples were . analyzed by XRD and Mossbauer spectroscopy. A satisfactory t was obtained using the binomial distribution model, suggesting a random substitution of iron ions by zinc in tetrahedral sites. The dependences of the hyperne magnetic elds and relative areas of the tetrahedral and octahedral sublattices were derived as function of the substitution level x. It

60

theory octahedral theory

40

20

0 0.0 0.2 0.4 0.6 0.8 1.0

Fig. 6. Dependence of the sublattice areas on the Zn substitution level x for NiZn ferrites synthesized from hematite.

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M. Sorescu et al. / Journal of Magnetism and Magnetic Materials 279 (2004) 195201
Ni1-xZnxFe2O4 ( from magnetite )
100

201

80

Sublattice area (%)

60

tetrahedral theory octahedral theory

40

No. DE-FC26-02NT41595. However, any opinions, ndings, conclusions, or recommendations expressed herein are those of the authors and do not necessarily reect the views of DOE. The authors R.P. and R.R. would like to acknowledge DARPAs support for Microwave Science at MRL via Grant No. N00014-981-1-0752. P.Y. wishes to thank Department of Science and Technology (Government of India) for awarding BOYCAST fellowship.

20

References
0 0.0 0.2 0.4 0.6 0.8 1.0

Fig. 7. Dependence of the sublattice areas on the Zn substitution amount x for NiZn ferrites synthesized from magnetite.

has been established that, in most cases, the hematite precursor leads to higher values of the hyperne magnetic elds. This study sheds light on the structureproperty relationships in ferrites.

Acknowledgements The work at Duquesne was supported by the US Department of Energy, under Award

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