International Journal of Scientific Research Engineering & Technology (IJSRET), ISSN 2278 0882

Volume 4, Issue 2, February 2015

Structural Parameters of Mo6+ Substituted Lithium Ferrites

M.V.K.Mehar1, U.V.B.B.K.Prasad2, K.Venkateswara Rao3, K.samatha4
1,2,3
Lecturers in Physics, P.R. Govt. College (A), Kakinada, A.P., India
4
Professor of Physics, Andhra University, Visakhapatnam, India.

Abstract
High valancy molybdenum substituted lithium ferrites with compositional formula [Li(1+3y)/2MoYFe2.5-5y/2]O4 (where y
= 0.1 to 0.5 insteps of 0.1) were prepared under standard ceramic method. The bulk and theoretical densities were found.
Bulk and theoretical densities were gradually decreases with increasing substituent concentration (y). From X-ray studies
the spinel structure and belonging Fd3m spce group is confirmed. The lattice parameter was found to increase gradually
except for the sample with y=0.3 for which it slightly decreases with continuous increasing molybdenum substituent
concentration. The other parameters like oxygen positional parameters, tetra hedral and Octahedral bond lengths, tetra
hedral edge, shared and unshared octa hedral edge lengths were calculated and found to be increasing with substituent
concentration except for y=0.3 sample.

I.

INTRODUCTION

Lithium ferrites belong to the class of soft ferrites and have potential applications in electrical components, memory
devices over a wide range of frequencies due to their highest Curie temperature, excellent rectangular loop
characteristics, high resistivity, low eddy current losses, low dielectric loss and high Neel temperatures, superior
temperature stability of saturation magnetization, low intrinsic line width and low magnetic losses[1-3]. They have
excellent flat profile of permeability at high frequencies along with high dielectric constant. In addition to the properties
rapidly changes with variation in composition, ease of fabrication and low cost they offer better performance over other
ferrites.
[Li0.5Fe2.5]O4 is an inverse spinel with the Li1+ and three fifths of the Fe3+ ions occupying the octahedral B sites of
the cubic spinel structure of the general formula AB2O4 [4]. Since the number of ferric ions on A and B sites is unequal the
magnetization of the sample is given by the difference in the magnetic moments of ions on A and B sites. Consequently,
lithium ferrite possesses a higher Curie temperature than other spinel ferrites [5] and other advantages suitable for
applications.
The present paper discusses the variation of lattice constants, density, porosity and other structural parameters with
substituent concentration. The lattice constant values give the information on the bond lengths which determine the
exchange interactions and chemical interactions.

II.

EXPERIMENTAL DETAILS

The prepared samples with compositional formula [Li(1+3y)/2MoyFe2.5-5y/2]O4 (where y =0.1, 0.2, 0.3, 0.4 and 0.5)
were prepared by conventional standard ceramic method. The appropriate proportions of Li 2CO3,Fe2O3 and MoO3 were
taken and thoroughly mixed in an agate mortar in the presence of methanol. The dried mixture was pre-sintered at 625 oC
for 4 hrs. The related powder was ground again and granulated using a small amount of PVA binder. Finally granulated
powder was compressed uniaxially under pressure of 5 tones/cm2 in a stainless steel die to make pellets and the samples
were sintered at 1200oC for 4hrs for good densification. The samples were cooled in the furnace in air atmosphere at the
rate of 30C/min. Due to sintering at 1200 0C lithium volatility occurs and as a result Fe2+ ions exist [6]. Some of the
properties are more attractive when sintering at 1200 oC than sintered at 1000 oC [7-9].
Theoretical density (dx) of the samples were calculated by using formula
8
(dX) = 3 gm/cm3 [10]
(1.1)

Where
=Lattice Parameter
8 = Number of molecules in a unit cell of a spinel lattice
M = molecular weight in gram mole of the spinel
N = Avogadro number (6.02251023 atom/mole).
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International Journal of Scientific Research Engineering & Technology (IJSRET), ISSN 2278 0882
Volume 4, Issue 2, February 2015

The bulk density (dob) of the samples was measured through the Archimedes principle. The lattice parameter of the
samples was determined using PHILIPS (Xpert: Japan) diffractometer in the range between 15o to 80o at room
temperature. The Cu-K radiation was used and scanning rate was 30/ minute.

III.

RESULTS AND DISCUSSION

The bulk density (dob) is found to be decreasing with increasing molybdenum concentration. When the molecular
weight increases with increasing concentration of molybdenum, the density decreases and this can be explained on the
basis of decreasing intermolecular forces. This can be understood in terms of sintering and other parameters. It is
observed that samples become slightly hygroscopic with increasing molybdenum concentration. Therefore, all the samples
were stored in a dessicator and handeld with care. The forming of the samples with molybdenum substitution is difficult
because they require sintering at 1200 oC and slow rate of cooling. From the above mentioned formula 1.1, lattice constant
is inversely proportional to the density. This can be attributed to the densification of the material and depends on the
sintering, rate of cooling and heating, furnace atmosphere etc. The -ray density is found to exhibit higher value when
compared with its bulk density for all samples. The X-ray densities (theoretical densities) are also decreases. The bulk and
X-ray densities are almost agrees with reported values [11]. The variation between these can be related to the porosity
differences in materials. Bulk and theoretical densities are listed in Table 1.
Lower porosity is required for good quality ferrites material and larger porosity affects physical properties of the
material. High valancy cations create cation vacancies, microvoids and bulk diffusion of cations contribute to the increase
in percentage of porosity [12]. Since the charge balance is effected by the creation of vacancies, the porosity is found to be
more for these ferrites which have high valancy cations as substituents.
From X-ray diffrectrometer, the lattice parameter were calculated and are in good agreement for y=1.0 with standard
JCPDS data card number 72-1911.
Some of the typical spectra are shown in the Fig. 1. The patterns of all the samples exhibited lines corresponding to
single phase spinel structure for Mo6+ substituted lithium ferrites. The important peaks of planes (111), (311), (222),
(400), (422), (511), (440) and (531) confirm the presence of single phase with face-centered cubic structure [13].
The obtained lattice constant (8.3453 ) is an agree with the reported values (8.316 ) [11,14-15] of basic ferrite. The
values of lattice constant (a) are computed using the standard extrapolation method (Nelson-Riley function) [16] with
error error 0.0019 .
The lattice constant ( ) values of molybdenum substituted ferrites are given in the Table 1. It shows that the
compositional variation of lattice constant is increasing with increasing of molybdenum concentrations. The ionic radius
of Mo6+(0.62) is smaller than the Fe3+ (0.64). So it is expected that the lattice constant decreases with the increase of
y . Contrary to this, in the present studies that the lattice constant increases with the increase of y except for y= 0.3.
This may be due to cation distribution in A and B site for this composition.
One factor which would influence this behavior is the higher charge of substituents ions. This can be explained on
the basis that ionic radius of Li1+(0.68 ) is greater than ionic radius of Fe3+ (0.64 ) which it replaces at A site. The Mo6+
ions seems to replace the Fe3+ at B site. When Li1+ is added, the Fe3+ moves from A site to B site. Therefore, lattice
constant increases. The similar behavior with Mo6+ was observed from earlier[17-18] .
Further this can be explained as lithium ferrites exist in two different crystalline forms [19]. The phase with FCC
inverse spinel structure and space group P4332 in which all Li1+ ions and 3/5 of all Fe3+ ions occupy the octahedral Bsites in an ordered fashion whereas the remaining Fe3+ ions occupy the tetrahedral A sites. The -phase is a similar
structure except that Li1+ and Fe3+ ions are randomly distributed in the octahedral interstices and space group is Fd3m.
Therefore, it is supports the above observations of increasing lattice constant as Li1+ replaces Fe3+.
Using the lattice constant a, we can calculate some other structural parameters also i.e. inter ionic distances, tetra
hedral and octa hedral bond lengths etc. have been computed and presented in the Table 2 with the following formulae
[18,20-21] :

= a3
a

= a2

u4

32
1
2 2

11

(2.1)
+

43
64

1
2

(2.2)
(2.3)

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International Journal of Scientific Research Engineering & Technology (IJSRET), ISSN 2278 0882
Volume 4, Issue 2, February 2015

=a 2 1 2
= a 42 3 +

(2.4)
11 1/2
16

(2.5)

Where u is the oxygen positional parameter values are calculated [22-23]

and listed in the Table 2.
represent the tetra hedral and octahedral bond lengths. , are the tetra hedral edge, shared and
unshared octa hedral edge lengths. From the Table 2 the oxygen parameters u of molybdenum substituted lithium ferrites
increases. All the , , , values are increased except for y= 0.3 is decreased. This is attributed to the
fact that y=0.3 lattice parameter is decreases.

IV.

CONCLUSION

The bulk and X-ray densities were calculated and the differences between them were discussed. The bulk density is
found to decrease with gradual increasing of molybdenum concentration. The X-ray densities were calculated and found
to decreases with continuous increasing of y. The changes in density with substituent concentration is attributed to
sintering conditions. The differences between the bulk density and theoretical densities are attributed to porosity. Porosity
of the samples was calculated and found to be increasing from 7.5 to 29.5 % . - ray diffraction pattern of all the samples
confirm single phase spinel structure without any evidence of unreacted ingredients. - ray diffraction pattern of lithium
ferrites confirm the - phase with space group Fd3m.The lattice constant is found to be increasing with increasing
molybdenum substituent concentration except for y=0.3 where it decreases.Oxygen positional parameters, tetrahedral and
octahedral bond lengths, tetetrahedral edge, shared and unshared octahedral edge lengths been evaluated and these are
found to be increasing except for y=0.3 sample where they decrease slightly.

REFERENCES
[1] Ernst Scholoeman, Advances in ferrite microwave materials and devices, J. Magn, Magn., Mater. 209 Jan.2000 pp.
15-20.
[2] Sun-Ho Kang, Han-Ill Yoo,Nonstoichiometry () and High-Temperature Thermodynamic Properties of
(Mg0.22Mn0.07Fe0.71)3O4, J. Solid State Chem., 145 Feb.1999 pp.276-282.
[3] M. Abe, J. Kuroda, M. Matsumoto, Granular composites containing micro-onions, permeability, and permittivity
calculated for application to microwave absorbers, J. Appl. Phys, 91 (10) May 2002 pp. 7373 -7375.
[4] S. Verma, P.A. Joy, Magnetic properties of
super paramagnetic lithium ferrite nanoparticlesJ. Appl. Phys.
Vol.98 Dec. 2005,pp. 124312 -124312-9.
[5] Yen-PeiFu, Microwave induced combustion synthesis of Li0.5Fe2.5xCrxO4 powder and their characterization,
Mater. Res. Bull., Vol. 41, Oct.2005, pp. 809-816.
[6] Yen-PeiFu, Shao-Hua Hu, Electrical and magnetic properties of magnesium-substituted lithium ferrite, Ceram. Int.
Vol.36, Jan. 2010, pp.1311-1317.
[7] D. Ravinder, "Elastic behaviour of lithium ferrites", Mater. Lett., 45(2), March 2000,pp. 125-127.
[8] S.Manjura Hoque, M. Samir Ullah, F.A. Khan, M.A.. Hakim, D.K. Ssha, Strucural and Magnetic properties of LiCu mixed spinel ferrites Physica B, Vol. 9 Feb.2011,pp. 1799-1804.
[9] Nutan Gupta, Mukesh C. Dimri, Subhas C. Kashyap, D.C. Dube, Processing and properties of cobalt-substituted
lithium ferrite in GHz frequency rang, Ceram. Int., Vol. 30, April 2004, pp. 1623-1628.
[10] J. Smith, and H.P.J. Wijn Ferrites , Philips Technical Library, Eindhoven, The Netherlands (1959).
[11] S. S. Bathu, V. K. Lakhani, A.R. Tanna, N. H. Vasoya, J. U. Buch, P. U. Sarma, U. N. Trivedi, H. H. Joshi and K.
B. Modi, Effect of nickel substitution on structural, infrared and elastic properties of lithium ferrite Indian J. Pure
Appl. Phys., Vol.45 April 2007, pp. 596-608.
[12] A. D. P. Rao, Ph. D thesis, structural,magnetic and electrical studies on Sn/Nb substituted Mn-Zn ferrites
Submitted to Andhra University, India,1995.
[13] M. Goodarz Naseri, E. Bin Saion, H. Abbastabar Ahangar, M. Hashim, A. H. Shaari, Synthesis and characterization
of manganese ferrite nanoparticles by thermal treatment method J. Magn. Magn. Mater., vol.323Feb.2011, pp. 17451749.
[14] A. B. Naik, S. R. Sawant, S. R. Sawant, S. A. Patil and J. I. Power, On the variation of a.c. susceptibility with
temperature for some Cu-Li ferrite, Bull. Mater. Sci., Vol. 11(4) Dec.1988, pp. 315-318.

www.ijsret.org

123

International Journal of Scientific Research Engineering & Technology (IJSRET), ISSN 2278 0882
Volume 4, Issue 2, February 2015

[15] S. B. Murthy and T. S. Rao, Phys. Stat. Sol., Elastic behaviour of mixed Li-M ferrites, Physica stat. solidi(a), Vol.
88, March 1985,pp. 239-243.
[16] B. C. Cullity, Elements of -ray Diffraction Addison-Wesely , Publishing Co. Inc (1959).
[17] K. S. Laksmi, B. Ramesh, A. D. P. Rao, P. M. RAo and S. B. Raju, Effect of Sb/Mo on magnetic properties of MnZn ferrites J. Mag. Soc. Japan, Vol. 22, Supp. S1, 1998, pp. 37-40.
[18] D.Vijayalakshmi,Ph.Dthesis, Structural,Magnetic and Mssbauer studies of antimony and molybdenum substituted
Mg-Mn ferrites Submitted to Andhra University, India, Nov.2003.
[19] H. M. Widatallah, C. Johnson, F. J. Beerry, A. M. Gismelseed, E.Jartych, J. F. Marco, F. S. Gard, M. Pekala,
Synthesis and cation distribution of copper-substituted spinel-related lithium ferrite, J. Phys. Chem. Solids,Vol. 67
April 2006, pp.1817-1822.
[20] C. Oetro Arean, J. L. Rodriguez Balnco, J. M. Rubio Gonzalez and M. C. Trobajoa
Fernandez Structural
characterization of polycrystalline gallium-substituted cobalt ferrites'J. Mater. Lett, Vol.9,Feb.1990 pp. 229-230.
[21] R. L. Dhiman, S. P. Taneja and V. R. Reddy Structural and Mssbauer Spectral Studies of Nanosized Aluminum
Doped Manganese Zinc Ferrites Adv. Cond. Matter. Phys., Vol.2008 Nov.2008, ID 839536, 7pages
[22] K. B. Modi, J. D. Gajera, M. C. Chhanbar, K. G. Baldha, H. H. Joshi,
Structural properties of magnesium and
aluminium co-substituted lithium ferrite Mater. Lett., Vol. 57, Feb.2003, pp. 4049-4053.
[23] K. B. Modi, J. D. Gajera, M. P. Pandya, H. G. Vora and H. H. Joshi,
Far infrared spectral studies of
magnesium and aluminium co-substituted lithium
ferrites, Indian. Acad. Sci., Vol. 62(5). Jan. 2004 pp. 1173-1180.

Table: 1
Variation of lattice parameter (a), X- ray density (dx ), experimental density (dob) along with porosity of the ferrites as a
function of molybdenum (y)

S.No

Substituent
Lattice
Concentration parameter (a)
(y)

1
2
3
4
5

0.10
0.20
0.30
0.40
0.50

()
8.3453
8.3582
8.3204
8.3817
8.4004

Density
( dob)
gm/cm-3

Density
(dX)

Porosity

gm/cm-3

4.3087
3.9702
3.7116
3.5151
3.0067

4.6564
4.5593
4.5450
4.3710
4.2673

7.5
12.9
18.3
19.6
29.5

Table: 2
Oxygen positional parameters, tetra hedral, octa hedral bond lengths, tetrahedraledge, shared and unshared octahedral
edge of Li-Mo ferrites as a function of substituent concentration.
S.No

1
2
3
4
5

Substituent
Concentration
(y)
0.10
0.20
0.30
0.40
0.50

dAL

dBL

dAE

()

()

()

()

0.26020
0.26040
0.26060
0.26080
0.26100

3.6136
3.6192
3.6028
3.6294
3.6375

6.8405
6.8510
6.8201
6.8703
6.8856

5.9010
5.9101
5.8834
5.9268
5.9400

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dBE
()
11.8020
11.8202
11.7668
11.8535
11.8799

dBEu
()
6.9196
6.9303
6.8989
6.9497
6.9652

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International Journal of Scientific Research Engineering & Technology (IJSRET), ISSN 2278 0882
Volume 4, Issue 2, February 2015

Fig.1: X-ray diffraction patterns of [Li(1+3y)/2MoYFe2.5-5y/2]O4 ferrites, where y =0.1,0.3 and

0.5.

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