Materials Letters 59 (2005) 2630 2633

www.elsevier.com/locate/matlet

Low-temperature synthesis of nanocrystalline powders of lithium ferrite

by an autocombustion method using citric acid and glycine
Seema Verma, Jayshri Karande, Arti Patidar, P.A. Joy*
Physical and Materials Chemistry Division, National Chemical Laboratory, Dr. Homi Bhabha Road, Pune 411008, India
Received 27 November 2004; accepted 7 April 2005
Available online 2 May 2005

Abstract
Nanocrystalline lithium ferrite is synthesized by an autocombustion method from the corresponding metal nitrates using citric acid as well
as glycine as fuels. The ordered phase of lithium ferrite, in single phase form, with particle size of 32 36 nm and large coercivity, is obtained
by this method at a low temperature of 200 -C.
D 2005 Elsevier B.V. All rights reserved.
Keywords: Low-temperature synthesis; Combustion synthesis; Nanomaterials; Magnetic materials; Lithium ferrite; LiFe5O8

1. Introduction
Lithium ferrite (Li0.5Fe2.5O4 or LiFe5O8) is a spineltype ferrite of the general formula AB2O4. Because of its
high saturation magnetization, high Curie temperature and
square loop properties, this ferrite is widely used in
microwave communications and memory core applications
[1]. Unlike other spinel-type ferrites, lithium ferrite exists
in two different crystalline forms [2]. The a-phase is an
ordered phase wherein the Li and Fe ions are ordered in
the 1 : 3 ratio in the octahedral sites of the cubic spinel
structure whereas the h-phase is a disordered phase where
the Li and Fe ions are randomly distributed in the
octahedral sites. During the usual ceramic method of
synthesis of the bulk ferrite, a slow cooling process from
above 755 -C yields the ordered phase whereas the
disordered phase can be obtained by quenching from high
temperatures. An order disorder phase transition takes
place in the temperature range 735 755 -C.
There have been few attempts to synthesize lithium
ferrite at low temperatures to take care of lithium
volatilization that occur during sintering at higher

* Corresponding author. Tel.: +91 20 2589 3300; fax: +91 20 2589 3044.
E-mail address: joy@dalton.ncl.res.in (P.A. Joy).
0167-577X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.04.005

temperatures and for improved microstructure and densification [3]. Interest in the study of nanosized ferrite
materials stems from their importance in many applications such as ferrofluids, magnetic carriers for sitespecific drug delivery, local hyperthermia and contrast
enhancement of magnetic resonance imaging [4 6].
Nanosized ferrite particles exhibit unusual magnetic
properties, which are not observed in the bulk, such as
single domain behavior, superparamagnetism and reduced
magnetization [7,8]. The citrate gel method is a well
known method for the synthesis of ferrite nanoparticles,
where the decomposition of a metal-citrate gel at lowtemperatures forms the required ferrite [9,10]. There are
some recent reports on the synthesis of lithium ferrite
nanoparticles at low temperatures by the citrate method.
However, different results are obtained though the
syntheses were made under identical conditions [11,12].
It has been shown that the disordered h-phase of lithium
ferrite, with a particle size of 10 nm, is formed at 200
-C which is converted to the ordered a-phase on heating
at 350 -C with a large increase in the particle size [11].
On the other hand, in another report, nanoparticles of the
disordered h-phase of size 10 and 20 nm are obtained by
decomposition of the citrate gel at 300 and 500 -C,
respectively [12]. Our studies show that the nanoparticles
formed at low temperatures, from the decomposition of

S. Verma et al. / Materials Letters 59 (2005) 2630 2633

the dried citrate gel, is actually Fe3O4 with minor

amounts of a-Fe2O3 as an impurity phase and this
powder on annealing at 600 -C forms the ordered phase
of lithium ferrite but with the a-Fe2O3 impurities still
present. However, we have synthesized the pure a-phase
of lithium ferrite by a simple autocombustion of the
metal nitrate/citric acid mixture at a low temperature of
200 -C and identical results are obtained when glycine is
used as the fuel instead of citric acid.

2631

(b)

2. Experimental

(a)
Lithium ferrite was synthesized from AR grade
chemicals by the following steps. Aqueous solutions of
metal nitrates in the required molar ratio, glycine and
citric acid were prepared. The metal nitrates and citric
acid (glycine) solutions were mixed in the metal to citric
acid (glycine) molar ratio of 1 : 1. The solutions were
slowly evaporated on a laboratory hot plate kept at 200
-C. A thick viscous gel that formed underwent combustion immediately producing a powder. In another case, the
metal nitrates citric acid solution was slowly evaporated
on a water bath to form a viscous gel. Further drying was
carried out in an oven at 110 -C to remove the adsorbed
water completely. During this process, the gel swells into
a fluffy mass, which eventually breaks into little fakes.
The dried gel was decomposed in a furnace at 300 -C and
the powder formed was kept at the same temperature for
4 h and was further annealed at 600 -C for 4 h. The asdecomposed and annealed samples were characterized for
phase purity and crystallinity by powder X-ray diffraction
measurements (Philips, PW-1730) with CuKa radiation
using Ni filter. Magnetic measurements were carried out
using a PAR EG & G 4500 vibrating sample magnetometer (VSM).

3. Results and discussion

Fig. 1 shows the powder X-ray diffraction patterns of lithium
ferrite powders synthesized by the usual decomposition of the
citrate gel and annealed at 300 and 600 -C. The XRD pattern of
the powder obtained at 300 -C is extremely broad, indicating that
the ferrite particles formed are extremely small. The average
crystallite size was calculated from the XRD line broadening
using the Scherrer relationship, d = 0 . 9 k / b cos u, where d is the
, b is the half maximum line width of the
crystallite size in A
peak and k is the wavelength of X-rays [13]. The average
crystallite size of the ferrite particles formed is obtained as 9 nm.
The XRD pattern of this sample is identical to that reported by
Dey et al. [12], who have reported that the disordered phase of
lithium ferrite is formed at this temperature. However, a closer
examination of the pattern indicated the presence of a very weak
reflection which corresponds to the most intense reflection from
a-Fe2O3. Moreover, the cubic lattice parameter is obtained as
, which is larger than that of h-LiFe5O8 (8.33 A
) [14] and
8.36 A

Fig. 1. Powder X-ray diffraction patterns of lithium ferrite synthesized by

the citrate gel method at 300 -C (a) and after annealing at 600 -C (b).

). When the powder sample is

is closer to that of Fe3O4 (8.38 A
heated to 600 -C, the pattern obtained corresponds to that of a , and the crystallite
LiFe5O8, with a lattice parameter of 8.33 A
size is increased to 40 nm. However, still the reflections due to aFe2O3 are clearly seen in the pattern, with increased intensities.
Approximately 7 10% of a-Fe2O3 is found in the sample
obtained at 300 and 600 -C, indicating that the a-Fe2O3 phase
formed initially is not converted to lithium ferrite on treatment at
600 -C. The increase in intensities of the peaks of the two phases
is due to the increased particle sizes of the ferrite and the aFe2O3 phases. The XRD pattern of the sample annealed at 600 -C
is comparable to that reported by Sankaranarayanan et al. [11],
where some additional weak and broad features are observed (but
not indexed).
Fig. 2 shows the powder X-ray diffraction patterns of lithium
ferrite powders obtained by the citric acid (CA) and glycine (GA)
autocombustion methods. In both cases, the reflections are
relatively sharp. This is due to the autocombustion nature of
the reaction where the flame temperature can be very high. Both
patterns are identical and all the reflections are due to the ordered
phase of lithium ferrite. No additional reflections due to a-Fe2O3
are observed indicating the formation of single phase material.
, for both
The cubic lattice parameter is calculated as 8.33 A
samples, from least-squares refinement, and is comparable to the
reported value for the ordered phase of lithium ferrite [14]. For
the samples obtained by the citric acid and glycine routes, the
average crystallite sizes are obtained as 32 and 36 nm,
respectively.
The magnetization as a function of field strength, recorded at
room temperature, for the two different Li ferrite samples
synthesized by the citric acid and glycine autocombustion routes
is shown in Fig. 3. The saturation magnetization at 10 kOe is
obtained as 37.5 and 43.9 emu/g, respectively, for the samples
synthesized using citric acid and glycine. The corresponding
coercivities are obtained as 130 and 160 Oe. Very large values
of the coercivity is obtained due to the single domain size limit
of smaller particles when compared to the reported small value

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S. Verma et al. / Materials Letters 59 (2005) 2630 2633

Fig. 2. Powder X-ray diffraction patterns of lithium ferrite synthesized by

the autocombustion method using citric acid (CA) and glycine (GA).

of the coercivity (< 20 Oe) for the bulk sample.The citrate gel
on decomposition and calcination at 300 -C produced the ferrite
with particle size of 9 nm and this sample shows typical
superparamagnetic behaviour at room temperature, where the
magnetization continuously increases with field without any
hysteresis, as shown in Fig. 4. However, XRD studies showed
that this sample is Fe3O4 and not lithium ferrite. On the other
hand, for the sample annealed at 600 -C, where lithium ferrite
is obtained with average crystallite size of 40 nm, the
magnetization is obtained as 47.2 emu/g, with a coercivity of
158 Oe.
The results indicate that it is difficult to obtain a pure
lithium ferrite phase by the usual citrate gel decomposition

Fig. 4. Magnetization as a function of the magnetic field, measured at room

temperature, for lithium ferrite samples obtained by the citrate gel
decomposition and annealed at 300 (CD300) and 600 -C (CD600).

method. On the other hand, an autocombustion method using

citric acid as well as glycine, single phase material of the
ordered a phase of lithium ferrite can be synthesized at a low
temperature of 200 -C in a single step. Usually this phase is
obtained by a slow cooling process from above 800 -C.
Nanoparticles of the ferrite in the single domain size limit of
30 40 nm can be obtained by this low-temperature method.
The ferrite formed shows very large coercivity due to the
nanocrystalline nature of the particles.

4. Conclusions
The ordered phase of the spinel lithium ferrite, aLi0.5Fe2.5O4, is synthesized in the nanocrystalline form by
an autocombustion method using citric acid as well as
glycine. Lithium ferrite nanoparticles, in single phase form,
with size 30 40 nm is obtained by this method at a low
temperature of 200 -C. Very large coercivities are obtained
for the ferrite nanoparticles when compared to that of the
bulk material.

Acknowledgements
S. V. is grateful to Council of Scientific and Industrial
Research, Government of India, for a research associateship.

References

Fig. 3. Magnetization as a function of the magnetic field, measured at room

temperature, for lithium ferrite samples obtained by the citric acid (CA) and
glycine (GA) autocombustion routes.

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