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Cation Distribution in Mixed Mg-Mn Ferrites from X-ray Diffraction Technique

and Saturation Magnetization

Article  in  Indian Journal of Pure and Applied Physics · December 2006

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Indian Journal of Pure & Applied Physics
Vol. 44, December 2006, pp. 930-934

Cation distribution in mixed Mg-Mn ferrite systems from X-ray diffraction

technique and saturation magnetization
Gagan Kumar, Meenakshi Kanthwal, B S Chauhan & M Singh*
Department of Physics, Himachal Pradesh University, Summer-Hill, Shimla-171 005,
Received 28 November 2005; revised 16 March 2006; accepted 12 October 2006

Ferrites with general formula Mg0.9 Mn0.1 Fe2-x Inx O4, Mg0.9 Mn0.1 Fe2-y Aly O4 and Mg0.9 Mn0.1 Al0.3 Coz Fe1.7-z O4
(where x, y = 0.0, 0.1, 0.3, 0.5 and z=0.3, 0.5, 0.7) were prepared by citrate precursor technique and studied by means of X-
ray diffraction and saturation magnetization. The X-ray analysis confirmed the single-phase formation of the sample. The
cation distribution is inferred from the results of X-ray diffraction and magnetization measurements.

Keywords: Ferrites, Cation distribution, Saturation magnetization, Magneton number

IPC Code: H0SH

1 Introduction ferrites at much low temperature. The method

Mixed metal oxides with iron (III) oxide as their
main component are known as ferrites. Spinel ferrites
are technologically important class of magnetic
oxides because of their good magnetic properties,
high electric resistivity, low eddy-current loss and low
dielectric loss. The Mg-Mn ferrites are quite versatile
from the point of view of their applications and
simplicity of their preparation. These ferrites have a
rectangular hysteresis loop characteristics making
them highly suitable for the use in memory and
switching circuits of digital computers, and as phase
shifter. Their interesting chemical and physical
properties arise from ability to distribute cations
among the available tetrahedral (A) and octahedral
(B) sites. In the present study, we investigated the
effect of substituted ions In3+, Al3+ and Co2+ in Mg-
Mn ferrite so as to calculate the cation distribution by
using X-Ray diffraction and magnetization studies.
2 Experimental Details
The performance of any ferrite is greatly
influenced by its synthesizing technique. The quality
of ferrites powder has strong influence on the
performance of the final device. In our case, all the
samples of mixed Mg-Mn ferrite were prepared by
citrate precursor method1-3. The main advantages of
citrate precursor method are that it is simple,
inexpensive and results in superior properties of
_________________
E-mail: *msv_phy_hpu@yahoo.com
involves the preparation of citrate complexes of the
constituent metal ions and mixing them in the solution
form. Subsequent decomposition of the derived
precursor mixture results in the formation of ferrite at
temperatures as low as 100°C. This low temperature
ferrite formation is attributed to the fine particle
nature of the oxides obtained during the citrate
decomposition leading to an increased reactivity. The
atomic scale mixing of the constituting cations by the
citrate precursor method results in better homogeneity
of the final ferrites composition. The samples were
prepared by using hydrated nitrates of the constituent
elements of purity 98%. The chemicals used were as:
(a) Mg (NO3)2.6H2O (>98%, Merck, India). (b) Mn
(NO3)2.4H2O (>98%, Merck, Germany). (c) In
(NO3)3.5H2O (>98%, Aldrich, Sweden). (d) Al
(NO3)3.9H2O (>98%, Merck, Germany). (e) Co
(NO3)2.6H2O (>98%, Merck Germany). (f) Iron was
in the form of iron citrate C6H5O7Fe.3H2O (>98%,
Merck, Germany). The solid state reactions used for
the preparation of the samples were as:
(1)0.9[Mg(NO3)2.6H2O]
+0.1[Mn(NO3)2.4H2O]+x[In(NO3)3.
5H2O]+ (2-x)[C6H5O7Fe.3H2O]
→Mg0.9Mn0.1Fe2-xInxO4;
x=0.0, 0.1, 0.3, 0.5.
(2)0.9[Mg(NO3)2.6H2O]+0.1 [Mn
(NO3)2.4H2O]+y[Al(NO3)3.9H2O]+
(2-y) [C6H5O7Fe.3H2O] → Mg0.9
 KUMAR et al.: CATION DISTRIBUTION IN MIXED Mg-Mn FERRITE SYSTEM 931

Mn0.1 Fe2-y Aly O4; y=0.0, 0.1, 0.3, 0.5. each sample at 300K were carried out using high field
(3)0.9[Mg(NO3)2.6H2O]+0.1 [Mn hysteresis loop technique4.
(NO3)2.4H2O] +0.3[Al (NO3)3.9H2O]
+z[Co(NO3)2.6H2O+(1.7-z) 3 Results and Discussion
[C6H5O7Fe.3H2O] → Mg0.9 Mn0.1 According to Bertaut5, Weil, Bertaut and Bochirol6,
Al0.3 Coz Fe1.7-z O4;z=,0.3, 0.5, 0.7. the best information on cation distribution in spinel
ferrites is achieved by comparing experimental and
The quantities of the reagents required for each theoretical intensity ratios for reflections (220), (440)
composition of a series were calculated from the and (422). According to Ohinishi and Teranishi7, the
above solid state reactions so as to prepare 30 g of intensity ratios of planes I220/I440 and I422/I440 are
each sample. In the present method, the required considered to be sensitive for the cation distribution
quantity of iron citrate was dissolved in ~50 ml of parameters. The distribution of cations among the A
distilled water by heating to 40°C and with constant and B sites in spinel has been experimentally proved
stirring. For the indium series, required amount of to an equilibrium function of temperature. In the
magnesium nitrate, manganese nitrate and indium present method, the ratio of intensities of reflections
nitrate were taken. These reagents were separately due to the planes (220), (440) and (422) has been
dissolved in ~40-50ml of distilled water by heating to chosen as a criterion to determine the cation
40°C and constant stirring. Now, the solution of distribution. The absorption and temperature factors
magnesium nitrate, manganese nitrate, indium nitrate are not taken into account in our calculation, because
were mixed together by heating to 40°C with constant these do not affect the relative intensity calculation
stirring. So the solution of these nitrates was then
added to the solution of iron citrate, and ~2-3 gm of
citrate acid (>99.5%). The composite solution was
heated at 40°C for about an hour with constant
stirring. It needs to be ensure that there is no loss of
material in the entire process. The precursor mixture
is then heated to 40°C with constant stirring, to allow
the water to evaporate, leaving behind a dried mass in
form of brown coloured glassy material containing the
constituents metal ions homogeneously mixed
together at the atomic level. The dried mixture was
scuppered and put on an alumina sheet and calcined
or presintered at 500°C for two hours. This
presintering process formed the ferrite crystals. The
mixture was allowed to cool to room temperature. A
few drops of polyvinyl alcohol were added as binder
and pressed into pellets under a pressure of ~ 10 tons.
These specimens were sintered in air in a box type
furnance at 1200°C for 1-2 hours and subsequently
cooled. The heating and cooling rate of ferrite was
maintained at ~ 2°C per minute. The single-phase
nature of the prepared sample was checked by X-ray
diffraction studies, which were made by Cu-Kα
radiation of wavelength 1.54 Å using Riga Ku-Denki
X-ray diffractometer and scanning electron
microscopy by Cambridge make Stereo Scan Electron
Microscope Model 360. The representative SEM’s
and X-ray patterns are shown in Figs 1 and 2, Fig. 1⎯Scanning electron micrographs of fractured surfaces for
respectively. The grain size of the samples is of the (a) Mg0.9Mn0.1Fe2-xInxO4, x=0.5; (b) Mg0.9Mn0.1AlyFe2-yO4, y=0.5
order of ~0.5 μm.The magnetization measurements of and (c) Mg0.9Mn0.1Al0.3CozFe1.7-zO4; z=0.5
932 INDIAN J PURE & APPL PHYS, VOL 44, DECEMBER 2006

Fig. 2⎯X-ray patterns of (a) Mg0.9Mn0.1Fe2-xInxO4, x=0.5; (b) Mg0.9Mn0.1AlyFe2-yO4, y=0.5; and (c) Mg0.9Mn0.1Al0.3Co2Fe1.7O4; z=0.5,
Powder calcined at 500°C and sintered at 1200°C

for spinel at room temperature8. To determine the
cation distribution, it is necessary to calculate for each
composition the intensity ratios I220/I440 and I422/I440
expected for given arrangement of the cations and
compare them with the experimental values. For the
calculation of the relative integrated intensity (I), of a
given diffraction line from powder specimen,
following formula is valid9.
Ihkl= |F|2hkl. P. Lp ... (1)
where F is structure factor, P multiplicity factor and
Lp is Lorentz polarization factor. The structure factor
F, is a function of oxygen parameter u, as well as
distribution parameter y. The formulae for the
structure factor of planes (hkl) are taken from those
reported by Furuhashi et al10. The multiplicity factor
and Lorentz polarization factors are taken from the
literature of BD Cullity11. The ionic scattering factor
reported in International Tables for X-ray
crystallography12, is used for the calculation of
 KUMAR et al.: CATION DISTRIBUTION IN MIXED Mg-Mn FERRITE SYSTEM 933

structure factor F. The distribution of the divalent
Mg2+, Mn2+ , Co2+ and trivalent Fe3+, Al3+, In3+
amongst octahedral (B) and tetrahedral (A) sites in the
mixed Mg-Mn ferrites system was determined from
the ratio of X-ray diffraction lines I220/I440 and I422/I440,
as given in Table 1. On the basis of Neel’s theory of
ferrimagnetism13, the Neel’s magnetic moment nB in
spinel ferrites is given by Eq (2)
nB= MB-MA … (2)
where MA and MB are the A and B sublattice magnetic
moments respectively. The values of magneton
number nB (saturation magnetization per formula unit
in Bohr magneton) at room temperature were
obtained, by using following relation14.
Sat. Magn. × Mol.Wt.
nB = emu/ gm
5585
Fig. 3 shows the variation of observed and
calculated values of magneton number (nB) with the
substitution of In3+, Al3+ and Co2+ ions in the mixed
Mg-Mn ferrites system. It had been conclusively
shown by Singh et al15. that when In3+ ions are
substituted in place of Fe3+ ions in Mg0.9 Mn0.1 Fe2-x
Inx O4 ferrite, the In3+ ions preferentially occupy
tetrahedral site. Thus, preference for In3+ ions to
occupy the A sublattice results in an increase of
magnetic moment of B sublattice and a decrease in
the value of magnetic moment of A sublattice. So the
net magnetic moment increases in accordance with
Neel’s two sublattice model13. The Al3+ ions
preferentially occupy B site16. The variation of
magnetic moment of Al-series can be explained as
above. In case of cobalt-series, the Co2+ ions
preferentially occupy B site17 but the variation of nB
with increasing substitution of Co2+ ions is attributed
to the high exchange interaction energy and relatively
higher orbital contribution of Co2+ ions for magnetic
moment18. The observed and calculated values are in
close agreement with each other.

Table 1⎯Cation distribution in mixed Mg-Mn ferrite systems

Mg0.9 Mn0.1 Fe2-x Inx O4

Composition Cation distribution I220/I440 I422/I440

Obs. Cal. Obs. Cal.
0.0 (Fe0.773 Mg0.162 Mn0.065)A 3.00 3.02 1.05 1.06
(Fe1.227 Mg0.738 Mn0.035)B
0.1 (Fe0.635 Mg0.2 In0.1 Mn0.065)A 3.10 3.03 1.23 1.36
(Fe1.265 Mg0.7 Mn0.035)B
0.3 (Fe0.505 In0.25 Mg0.180 Mn0.065)A 6.15 6.23 2.24 2.26
(Fe1.195 In0.05 Mg0.72 Mn0.035)B
0.5 (Fe0.335 In0.4 Mg0.2 Mn0.065)A 7.40 8.98 2.86 3.29
(Fe1.165 In0.1 Mg0.7 Mn0.035)B
Mg0.9 Mn0.1 Fe2-y Aly O4
A
0.0 (Fe0.773 Mg0.162 Mn0.065) 3.00 3.02 1.05 1.06
(Fe1.227 Mg0.738 Mn0.035)B
0.1 (Fe0.74 Mg0.18 Mn0.08)A 2.29 3.89 1.15 1.15
(Fe1.16 Mg0.72 Al0.1 Mn0.02)B
0.3 (Fe0.66 Mg0.16 Al0.10 Mn0.08)A 3.17 3.06 1.17 1.09
(Fe1.04 Mg0.74 Al0.2 Mn0.02)B
0.5 (Fe0.58 Mg0.14 Al0.2 Mn0.08)A 2.50 2.38 1.0 1.01
(Fe0.92 Mg0.76 Al0.3 Mn0.02)B
Mg0.9 Mn0.1 Al0.3 Coz Fe1.7-z O4
A
0.3 (Fe0.52 Mg0.2 Mn0.08 Al0.1Co0.1 ) 2.50 2.60 0.73 0.96
(Fe0.88 Mg0.7 Mn0.02 Al0.2 Co0.2)B
0.5 (Fe0.41 Mg0.21 Mn0.08 Al0.1 Co0.15)A 0.67 0.62 0.33 0.20
(Fe0.79 Mg0.64 Mn0.02 Al0.2 Co0.35)B
0.7 (Fe0.24 Mg0.28 Mn0.08 Al0.1 Co0.3)A 2.35 2.12 0.88 0.60
Fe0.76 Mg0.62 Mn0.02 Al0.2 Co0.4)B
 934 INDIAN J PURE & APPL PHYS, VOL 44, DECEMBER 2006

Fig. 3⎯Variation of observed and calculated values of magneton number (nB) with substitution of In3+, Al3+ and Co2+ ions

4 Conclusion 4 Murthy C R, Likhite S D & Sastry N P, Philos Mag, 23

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