Powder Technology 132 (2003) 131 – 136

www.elsevier.com/locate/powtec

A citrate process to synthesize nanocrystalline zinc ferrite from

7 to 23 nm crystallite size
A. Kundu a,*, S. Anand b, H.C. Verma a
a
Department of Physics, Indian Institute of Technology, Kanpur 208016, India
b
Regional Research Laboratory, Bhubaneswar 751013, India
Received 30 May 2002; received in revised form 18 December 2002; accepted 10 February 2003

Abstract

Nanosized zinc ferrite of controlled crystallite size has been prepared by calcining an amorphous zinc – iron – citrate precursor at different
temperatures up to 650 jC. The variation of crystallite size with calcination temperature has been investigated using X-ray diffraction (XRD),
thermogravimetry – differential thermal analysis (TG – DTA), and transmission electron microscopy (TEM), and a recipe for the preparation of
nano zinc ferrite of desired size has been developed. Zinc ferrite has been found to crystallize at temperatures as low as 200 jC and
calcination time as little as 1 h. The crystallite size varied from 7 to 23 nm as the calcination temperature was increased from 200 to 600 jC. It
has been observed that the crystallization of zinc ferrite from the amorphous powder is complete at 350 jC, forming 7-nm crystallites.
Calcination at higher temperatures leads to a linear growth of the crystallites from 7 nm at 350 jC to 23 nm at 600 jC.
D 2003 Elsevier Science B.V. All rights reserved.

Keywords: Citrate; Zinc ferrite; Crystallite size

1. Introduction tetrahedral and octahedral sites, making the interpretation of

Ferrites are interesting and technologically important
ceramic materials that have been extensively studied and
used for decades. In the last few years, the development of
nanotechnology has created a renewed interest in ferrites
because of the possible new technological applications in
areas like catalysts, suspension materials in ferromagnetic
fluids, and high-density ferrites. In addition, the structural
and magnetic properties of these nanoferrites are found to be
different from those of the bulk, in some cases [1– 6]. The
properties of spinel ferrites depend crucially on the cation
distribution in the available tetrahedral and octahedral sites
in the spinel lattice [7,8]. Although the simple single-
magnetic cation ferrites like zinc ferrite do not have exten-
sive application, they offer a simple system to study the
effect of cation site occupancy on the magnetic properties.
In this respect, zinc ferrite is particularly important because
of the strong tetrahedral site preference of zinc ions in zinc
ferrite. In contrast, the mixed ferrites with multiple magnetic
cations often show inversion so that the cations occupy both
* Corresponding author. Fax: +91-512590914.
E-mail address: ani_k@indiatimes.com (A. Kundu).
experimental data difficult. It was observed in nanosized
ferrites that the preference of cations for octahedral and
tetrahedral sites changes as the crystallite size decreases [7].
Thus, a fraction of zinc atoms was shown to have occupied
the octahedral sites against their strong preference for
tetrahedral sites in 12-nm Mn0.65Zn0.35Fe2O4 [9]. This led
to the unusual phenomena of appearance of superparamag-
netism on heating. In another report [10], it was shown that
the magnetic susceptibility of 4-nm zinc ferrite prepared
hydrothermally was about two orders of magnitude higher
than typical paramagnetic substances. This suggested the
presence of a strong magnetic interaction between Fe – Fe
neighbours, again indicating the occupancy of octahedral
sites by a fraction of zinc atoms. A host of different
techniques has been reported for the synthesis of nano-
ferrites [1 –13]. The ceramic method [6,8,11], in which the
components are thoroughly mixed and calcined at elevated
temperatures to get the crystalline product, is the most
common for the preparation of ferrites, but the high temper-
atures involved lead to grain growth. Other methods that
have been reported are high-energy ball milling [6], sol – gel
[4], coprecipitation from salts followed by calcinations at
high temperatures [1 – 3,7] and hydrothermal routes
[5,9,10,12]. Recently, the liquid mix process (the so-called

0032-5910/03/$ - see front matter D 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0032-5910(03)00049-4
132 A. Kundu et al. / Powder Technology 132 (2003) 131–136
Pechini process) has also been successfully used for the
preparation of zinc ferrites [13]. In this process, an inter-
mediate precursor of zinc and iron has been formed using
citric acid and ethylene glycol, which, on calcination, breaks
down to give the ferrite.
It is clear that studying and developing a process that can
produce zinc ferrite of desired crystallite size in the nano-
meter scale is of immense importance for understanding the
cation distribution in nanosize spinel ferrites and the effects
on observable properties. In the present investigation, we
synthesized zinc ferrite by calcination of a zinc – iron –
citrate precursor and studied the correlation of the crystallite
size with processing parameters. The process allows a good
control over the crystallite size so that a recipe could be
developed to get powders of desired crystallite size in the
nanometer range. The samples prepared were studied using
X-ray diffraction (XRD), transmission electron microscopy
(TEM), and thermogravimetry – differential thermal analysis
(TG –DTA). A unique feature of the procedure we adopted
is that the ferrite formation takes place at a very low
temperature (about 200 jC) and in a short calcination time
(1 h).
2. Experimental
A schematic of the synthesis route is given in Fig. 1. The
starting materials were ferric citrate, zinc acetate, and citric
acid. Aqueous solutions of iron and zinc salts were prepared
separately (concentration of 0.5 mol/l each) by dissolving the
Fig. 1. Schematic of the synthesis process.
Table 1
Samples prepared and their codes
Sample code Calcination temperature
and time
ZFC raw Precursor powder
ZFC201 200 jC, 1 h
ZFC301 300 jC, 1 h
ZFC351 350 jC, 1 h
ZFC401 400 jC, 1 h
ZFC451 450 jC, 1 h
ZFC501 500 jC, 1 h
ZFC551 550 jC, 1 h
ZFC601 600 jC, 1 h
ZFC651 650 jC, 1 h
salts in water and under constant stirring to facilitate dis-
solution and then added together in stoichiometric propor-
tions. Citric acid solution (concentration of 0.5 mol/l) was
prepared separately and added to the aqueous salt solution
with cations to citric acid ratio of 1:4. The solution was then
heated to boiling and maintained at that temperature for 24 h
in a heating mantle under constant refluxing and stirring
conditions. The refluxed solution was then slowly cooled to
form a viscous liquid. Finally, the viscous solution was dried
at 100 jC for 24 h to form a brown fluffy mass, which was
crumbled to form the precursor powder. This precursor
powder was calcined at different temperatures from 200 to
650 jC for 1 h to get zinc ferrite; the sample codes have been
shown in Table 1. The calcinations were carried out in a
wire-wound furnace with a temperature stability of F 5 jC.
The XRD patterns of the samples were recorded with
SEIFERT ISO DEBYEFLEX 2002 under identical condi-
tions to minimize the experimental errors in the quantitative
analysis of crystallite size and crystallinity. Thermal analysis
of the calcined samples was carried out at 20 jC/min in an air
atmosphere up to 600 jC. TEM images of the samples were
taken using a JEOL 2000FX II Microscope.
3. Results and discussion
3.1. X-ray diffraction pattern
Fig. 2 shows the X-ray diffraction pattern of the samples
calcined for 1 h at different temperatures. These measure-
ments show that the precursor powder is completely amor-
phous and crystalline zinc ferrite starts forming at 200 jC.
Pure zinc ferrite phase has been formed in all the samples
calcined at temperatures 400 –650 jC, while samples pre-
pared by calcining at temperatures below 400 jC show
small amount of amorphous and intermediate phases. The
small peaks around 32j in the samples calcined at temper-
atures below 400 jC seem to be due to the formation of
some metastable phase that decomposes at higher temper-
atures. The samples prepared by calcining at temperatures
above 650 jC show the formation of a small amount of zinc
oxide that might have formed due to evaporation of ferric
 A. Kundu et al. / Powder Technology 132 (2003) 131–136
Fig. 2. X-ray diffraction patterns of the zinc ferrite powders prepared by
calcining at different temperatures as indicated in the figure. All samples
were calcined for 1 h.
oxide at higher temperatures. As the calcination temperature
is increased, the XRD peaks becomes sharper (the intensity
ratio of peaks to background noise increases; the full width
at half maximum decreases).
In order to determine the particle size from the broad-
ening of the XRD peaks, we recorded the diffraction
patterns of the most intense peak (311) under slow scanned
conditions. These patterns are shown in Fig. 3. The intensity
of the (311) peak increases with the increase in calcination
temperature, showing better crystallinity and/or larger
Fig. 3. X-ray diffraction patterns of (311) peaks of the zinc ferrite powders
prepared by calcining at different temperatures as indicated in the figure.
All samples were calcined for 1 h.
133
amount of crystallite phase. The intensity of the (311) peaks
of the powders was normalized with the intensity of the
(311) peak of the powder calcined at 650 jC for 1 h and
plotted against the calcination temperature in Fig. 4. This
gives an approximate idea about the crystallinity of the
sample. The figure can be divided into three regions. For
temperatures 0– 350 jC, the peak intensity increases slowly.
As the calcination temperature is increased from 350 to 500
jC, the intensity increases rapidly. Above 500 jC, it tends to
saturate. The intensity can increase either due to the for-
mation of a larger amount of crystalline ferrite, or due to an
increase in long-range ordering, for example, due to grain
growth. It appears that in region 1 shown in Fig. 4, an
increasing amount of zinc ferrite is formed from the pre-
cursor as the temperature is increased, whereas the crystal-
linity increases with temperature in regions 2 and 3.
The individual X-ray diffraction patterns were studied in
detail for the determination of crystallite size using the
Scherrer equation. Corrections were made for spectral width
and instrumental error using a standard technique [14]. The
variation of crystallite size with calcination temperature is
shown in Fig. 5. Here also, the plot can be divided into the
same three different regions as described before. In region I
(i.e., at temperatures V 350 jC), the crystallite size remains
almost constant at 7 nm. This observation, together with the
linear increase in X-ray peak intensity in this region (Fig. 4),
indicates that decomposition of the precursor powder in this
region gives rise to f 7-nm crystallites of zinc ferrite and,
as the calcination temperature is increased, the amount of
zinc ferrite formed increases. Between 350 and 500 jC, the
crystallite size increases from 7 to 23 nm almost linearly
with calcination temperature. The peak intensity also
increases rapidly in this zone (Fig. 4). We infer from these
observations that the decomposition of the precursor and
any intermediate compound that might have formed during
the low-temperature calcination is complete at 350 jC and
Fig. 4. Variation of normalized intensity of (311) peaks of zinc ferrite with
temperature.
134 A. Kundu et al. / Powder Technology 132 (2003) 131–136

calcination at higher temperatures gives rise to the growth of

the crystallites. As the crystallite size goes beyond 25 nm
(region 3 in Fig. 4), the XRD peak intensity saturates and
there is no appreciable peak broadening.

3.2. TEM micrographs

Fig. 6 shows typical TEM micrographs of the zinc ferrite

samples calcined at 500 and 600 jC for 1 h (i.e., in the
linear range; region 2). We find that the crystallite size is
fairly uniform and the average value of the crystallite size is
consistent with those obtained from XRD patterns using the
Scherrer formula.

3.3. Thermal analysis

Fig. 5. Variation of crystallite size of the zinc ferrite powders with cal-
cination temperature. To get more information about the decomposition proc-
ess, we performed TG – DTA analysis for the precursor
powder as well as the powders prepared by calcining the
precursor powder at different temperatures. Fig. 7 shows
typical TG – DTA curves obtained for samples calcined at
temperatures (a) 300 jC and (b) 450 jC. The shapes of the
curves are distinctly different for the samples calcined at
temperatures V 350 and >350 jC. We have noted such a
discontinuity in XRD also where the crystallite size
remained almost constant until 350 jC and increased rapidly

Fig. 6. TEM photographs of powders calcined at (a) 500 jC and (b) 600 jC Fig. 7. TG – DTA results of samples calcined at (a) 300 jC and (b) 450 jC
for 1 h. for 1 h.
 A. Kundu et al. / Powder Technology 132 (2003) 131–136 135

Table 2 of zinc ferrite of crystallite sizes 10 –11 nm formed by

TG – DTA results of various zinc ferrite samples
citrate precursor method with somewhat different process
Sample Weight loss (%) Endothermic peaks Total weight parameters. They used zinc nitrate as the starting zinc salt
code loss (%)
30 – 210 jC 210 – 600 jC 260 jC f 340 jC and the concentrations of the solutions were also different
ZFC raw 6.3 65.7 Present Present 72 from ours. Also the refluxing was done for 5 h. The
ZFC201 4.2 36.3 Present Present 40.5 precursor was heated to 620 jC for 8 h to get pure zinc
ZFC301 3.4 18.3 Present Present 21.7 ferrite. Their analysis showed formation of metal aconitate
ZFC351 2.2 13 Present Present 15.2
(220 –260 jC), hydrozincite (260 –320 jC), ZnO and Fe2O3
ZFC401 – – Absent Absent
ZFC451 – – Absent Absent (320 – 460 jC) as intermediate phases. In contrast, our
ZFC501 – – Absent Absent procedure results in the formation of zinc ferrite at temper-
ZFC551 – – Absent Absent atures as low as 200 jC and with a calcination time of only
ZFC601 – – Absent Absent 1 h. Any intermediate phases that have formed are only in
ZFC651 – – Absent Absent
small quantity and completely decompose below 400 jC.

beyond this temperature. Table 2 summarizes the results of 4. Conclusions

the thermal analysis. The samples ZFC201, ZFC301, and
ZFC351 show two endothermic peaks: one at f 260 jC and
the other at f 340 jC. These may correspond to the
formation of some intermediate phase and its decomposi-
tion. No such peaks are observed for samples ZFC401 to
ZFC651. This shows that the decomposition of the inter-
mediate phase is complete below 400 jC. The weight loss
measurement in thermogravimetric data also confirms this
trend. The endothermic peaks in DTA are accompanied by
weight loss. There is no weight loss in the samples calcined
at temperatures z 400 jC, showing that formation of zinc
ferrite is complete at 400 jC. The precursor powder shows a
weight loss of 72% when heated to 600 jC. We performed
chemical analysis of the precursor powder, which showed
an iron content of 11.9% and a zinc content of 6.9%. This
corresponds to the stoichiometric amount of zinc and iron
content in zinc ferrite within experimental uncertainties.
This means there was no loss of cations during the chemical
reaction and fluxing. If all the iron and zinc were used up in
forming zinc ferrite, one would get 25.7 g of zinc ferrite
from 100 g of the precursor powder. Thus, one expects a
weight loss of 74.3% on heating the precursor powder. The
weight loss of 72% found in the TGA for the precursor
powder (Table 2) is in good agreement with this expectation
within the experimental limits. As the precursor is calcined,
some zinc ferrite is formed and the weight loss, as observed
from TGA plots, decreases. As the calcination temperature
is increased, the weight loss decreases and becomes negli-
gible for samples calcined at temperatures 400 jC and
above. This again confirms our earlier results from XRD
that zinc ferrite starts forming at temperatures as low as 200
jC, the amount of the precursor decomposed to give the
ferrite increases with calcination temperature, and the com-
plete decomposition occurs at 400 jC. Beyond this, only the
crystallite size increases without any further loss in weight.
We have made no attempts to identify the intermediate
products, or to interpret what the two endothermic peaks
correspond to. The goal for the present work (i.e., to develop
a controlled process for nanosize zinc ferrite formation) is
achieved. Gajbhiye et al. [15] have reported DTA analysis
A chemical process is described to obtain single-phase
zinc ferrite powder of desired crystallite size. The synthesis
technique shows ferrite formation at a calcination temper-
atures as low as 200 jC and in a calcination time of 1 h.
However, small quantities of some intermediate phases
coexist at calcination temperatures V 350 jC. As the calci-
nation temperatures increases, more and more amounts of
precursor powder seem to form f 7-nm zinc ferrite powder
until the temperature has reached 350 jC. As the calcination
temperature is raised above 400 jC, the crystallinity
increases due to grain growth. The crystallite size increases
linearly from 7 nm to about 23 nm as the calcination
temperature is increased from 400 to 600 jC.
Acknowledgements
We thank Mr. Chandan Upadhyay of Department of
Physics, IIT Kanpur, for his active participation during the
work.
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