Powder Technology 192 (2009) 245–249

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Powder Technology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / p ow t e c

Low temperature synthesis of single-phase α-Fe2O3 nano-powders by using simple

but novel chemical methods
Prita P. Sarangi, Bhanudas Naik, N.N. Ghosh ⁎
Chemistry Group, Birla Institute of Technology and Science – Pilani, Goa Campus, Zuarinagar, Goa – 403726, India

a r t i c l e i n f o a b s t r a c t

Article history: Two simple chemical methodologies have been described for the preparation of single-phase α-Fe2O3 nano
Received 6 August 2008 powder with particle size ∼ 20–30 nm. Precursor powders were synthesized by reacting aqueous solutions of
Received in revised form 15 December 2008 ferric nitrate and PVA and sucrose (method 1) and EDTA (method 2) and then evaporating the resulting
Accepted 4 January 2009
solutions to dryness. The precursors were subsequently calcined in air for 2.30 hr at different temperatures
Available online 8 January 2009
ranging from 250 to 450 °C. The synthesized powders were characterised using TG-DSC analysis, X-Ray
Keywords:
Diffraction, BET surface area measurement, SEM and TEM. DC electrical resistivity of the synthesized
Nano-powders materials was measured by the two-probe method. The synthetic routes described here provide simple but
Chemical preparation cost-effective methods to produce single phase, α-Fe2O3 nanopowder at a comparatively low temperature.
X-ray methods © 2009 Elsevier B.V. All rights reserved.
Electrical properties
Iron oxide

1. Introduction
Nanoparticles of iron oxide, in its different phases, are being
currently explored for their diverse range of applications such as
magnetic storage media, environment protection, sensors, catalysis,
clinical diagnosis and treatment etc. The attention which is being
focused on their synthesis and characterization is well-deserved as
they have the capability to exhibit certain superior properties as
compared to bulk. In particular, superparamagnetic (SPM) nanopar-
ticles of iron oxide are being used in biotechnology and biomedicine,
as contrast agents in magnetic resonance imaging (MRI), as drug
carriers for magnetically guided drug delivery, biosensors etc [1,2].
The physical properties of nanomaterials greatly depend on their
surface characteristics and microstructure. These in turn are highly
sensitive to the phase and quality of the synthesized nanomaterial.
Hence, the importance of single phase material can not be under-
mined as it is crucial for the accurate measurement of physical
properties (such as electrical and magnetic properties). Iron oxide is a
well-known semiconductor having negative temperature coefficient
of resistance. The use of high resistance (~108 Ω) α-Fe2O3 thin films
as humidity sensor has been demonstrated by Chauhan et al [3].
However, in order to synthesize nano-sized iron oxide powders,
the traditional high temperature solid state route is inappropriate, as
it leads to coarsening of grains. In the pursuit to prepare homogenous
nanoparticles of iron oxide, a variety of synthesis routes like precursor,
precipitation, sol-gel, hydrothermal, combustion, solvent evaporation
[1–9] etc. have been utilized. Pramanik et al have developed polymer
⁎ Corresponding author. Tel.: +91 8322580318; fax: +91 8322557033.
E-mail address: naren70@yahoo.com (N.N. Ghosh).
based precursor method and metal complex (using tri ethanol amine)
precursor method for synthesis of variety of nanosized metal oxides
[10–13]. Ghosh et al have reviewed different synthetic methodologies
for preparation of ferrites [14]. Some typical examples are discussed
here. Raming et al have described a method to prepare nanocrystalline
hematite powder in which ferric chloride was allowed to hydrolyze at
100 °C for 1 week in presence of hydrochloric acid [1]. Zhong et al have
reported the synthesis of 3D flower-like iron oxide nanostructures by
a precursor route using ferric chloride, urea, tetrabutyl ammonium
bromide and ethylene glycol as starting compounds and decomposing
the precursor at 450 °C for 3 h [2]. Chauhan et al have prepared
nanocrystalline thin films of α-Fe2O3 by sol-gel method using
ethylene glycol mono methyl ether and iron nitrate and annealing
temperature 400 to 700 °C [3]. Hyeon et al have reported a reaction of
Fe(CO)5 with oleic acid and dehydrated (CH3)3NO in argon atmo-
sphere and hexane as medium to prepare maghemite [4]. Ganguli et al
have reported a reverse micellar route to synthesize iron oxalate
nonorods using cetyltrimethyl ammonium bromide as surfactant.
Spherical α-Fe2O3 nanoparticles were obtained by decomposition of
these nanorods at 500 °C [5].Cao et al have employed hydrothermal
technique to prepare micropine structure of α-Fe2O3 by autoclaving
K3[Fe(CN)6] for 2 days [6]. A nonhydrolytic precursor method was
described by Rockenberger et al where Fe(cupferron)3 was injected in
dry trioctylamine at 300 °C in argon medium [6].
However, most of the reported methods are associated with some
limitations such as use of (i) metal complex compounds as starting
materials, which are difficult to synthesize and expensive (ii) delicate
reagents those are difficult to handle (iii) and/or strong acids, bases,
(iv) sometimes use of organic solvents. Moreover, formation of mixed
or undesired crystalline phases often occurs during processing [15].

0032-5910/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.powtec.2009.01.002
246 P.P. Sarangi et al. / Powder Technology 192 (2009) 245–249
Therefore, development of a simple synthetic methodology for
preparation of pure and homogeneous α-Fe2O3 nanopowders is a
major challenge till now.
In order to overcome the limitations of the existing methods, we
have developed technically simple but cost effective chemical
synthetic routes. Herein, we report two synthesis methodologies for
preparation of single phase α-Fe2O3 nanopowders. In these methods
precursor powders were synthesized by reacting aqueous solutions of
ferric nitrate with PVA and sucrose (method 1) and EDTA (method 2).
Pure α-Fe2O3 nanopowders were obtained by calcining the precursor
powders at different temperatures ranging from 250 to 450 °C in air.
Calcined powders were characterized by using TG-DSC analysis, X-Ray
Diffraction, TEM, BET surface area measurement and SEM. Variation of
its DC electrical resistivity with respect to temperature has also been
measured as this material has the potential application as humidity
sensor.
2. Experimental Procedure
2.1. Chemical Synthesis
The starting chemicals used were ferric nitrate nonahydrate
(99.9%, Merck, India), EDTA (99.9%, Merck, India), Sucrose (99.9%,
Merck, India) and Poly vinyl alcohol (PVA, Mol. Wt. = 1,25,000) (S D
Fine Chemicals, India) without further purification. Distilled water
was used as solvent. Precursor powders were synthesized using the
following two methods.
2.1.1. Method 1
An aqueous solution of PVA (10 wt%) was prepared by dissolving
0.25 mole PVA in hot water. 0.1 mole ferric nitrate was dissolved in
150 ml of distilled water. These two solutions were mixed vigorously
by using a magnetic stirrer. An aqueous solution of sucrose (10 wt% of
sucrose with respect to PVA) was added to this mixture and stirred for
1 hr at room temperature. A dark brown colored fluffy precursor was
formed when this mixture was dried on a hot plate at ~ 125 °C.
Precursor powder prepared by this method will be referred hereafter
as “Precursor-1”.
2.1.2. Method 2
0.1 mole ferric nitrate was dissolved in 150 ml of distilled water
and mixed it with 100 ml aqueous solution of 0.1 mole EDTA. The
resulting mixture was stirred for 1 hr at room temperature using a
magnetic stirrer. A dark brown fluffy precursor was formed when this
mixture was evaporated on a hot plate. Precursor powder prepared by
this method will be referred hereafter as “Precursor-2”.
α-Fe2O3 nanopowders were prepared by grinding the precursor
powders, prepared by above mentioned methods, followed by
calcination in air for 2.30 hr at different temperatures ranging from
250 to 450 °C at a heating rate of 2 °C/ min.
2.2. Sample Characterization
TG and DSC analyses of the precursors were conducted using DTG–
60 and DSC–60 instruments from Shimadzu, Japan respectively. The
experiments were conducted under air flow between room tempera-
ture and 550 °C at a scanning rate of 20 °C/min. The sample pans were
in aluminum in both cases. The crystalline phases present in the
materials calcined at various temperatures were identified by XRD
using a Powder X-Ray Diffractometer (Mini Flex II, Rigaku, Japan) with
Cu Kα radiation. Scans were recorded in the (2θ) range of 20° to 70°
with a scan rate of 2° /min. The BET-specific surface areas of the
powders were measured by nitrogen adsorption using a Tri Star 3000
Surface Area Analyzer (Micromeritics, USA). The particle size for the
calcined powder was determined using a FEI HRTEM (Tecnai G2 30S-
Twin) at an accelerating voltage of 300 kV. Surface morphology of α-
Fe2O3 powder (pellet form) was characterized by using a JEOL (JSM
6560 LV) SEM operated at an accelerating voltage of 20 kV. DC
resistivity was measured from room-temperature to 225 °C by the
two-probe method using a Keithley Electrometer (6517 A). For this
measurement, calcined powder was pressed into a pellet of ~ 13 mm
diameter and ~ 2 mm thickness at a pressure of 3 tons. The pellet was
heat treated at 450 °C for 2 hours and then coated with silver paste on
both surfaces to make contacts.
3. Results and Discussion
3.1. Thermal Analysis
TG-DTG and DSC analysis was performed to investigate the
decomposition behavior of the precursor powders due to heat
treatment in air and thermogams are shown in Fig. 1. It was observed
that: (i) in case of precursor-1, the major weight loss of 51% occurred
in the region from 200 to 450 °C (ii) for precursor-2, two major weight
losses of ~48% and ~20% were observed in the temperature region of
140 to 350 °C and 355 to 460 °C respectively. These major weight
losses for both the cases were attributed to the oxidative decomposi-
tion of the organic components of the precursors leading to the
formation of iron oxide and evolution of NOx and CO2 gas during
decomposition. This decomposition was reflected in DSC as exother-
mic peaks at 326 °C for precursor-1 and at 286 and 415, 458 °C for
precursor-2. Heating the samples beyond 460 °C resulted in neither a
weight loss nor formation of any new peak. This confirmed the full
decomposition of the precursors to iron oxide at 460 °C.
3.2. X-Ray Analysis
Room temperature powder X-Ray Diffraction spectra for the
precursors and calcined powders were performed to identify the
crystalline phases present in the samples and shown in Fig. 2.
Presence of diffraction peaks in XRD spectra of the samples at
2θ = 24.1°, 33.1°, 36.0°, 40.8°, 49.4°, 54.0°, 57.4°, 62.4°, and 63.9° were
in good agreement with the corresponding (012), (104), (110), (113),
(024), (116), (018), (214) and (300) diffraction planes of α-Fe2O3
respectively and clearly indicate the formation of α-Fe2O3 phase [1].
The notable features observed were (i) formation of α-Fe2O3 phase in
precursor-2 without calcination, whereas precursor-1 was amorphous
in nature, (ii) pure α-Fe2O3 phase formed when precursors were
calcined at 250 °C and above, (iii) formation of any other phase such as
γ- Fe2O3 or Fe3O4 was not observed at any stage of calcination.
Crystallite size of the calcined powders was calculated using
Scherrer's equation [16] for (104) and (110) diffraction planes. They
Fig. 1. TGA-DSC thermograms of the precursors in air (- - - -) for Precursor-1 and ( P )
Precursor 2.
 P.P. Sarangi et al. / Powder Technology 192 (2009) 245–249 247

from the homogeneous precursor solution during evaporation. In case

of Method –II, the chelating/ complexing agent (EDTA) plays a dual
role. It not only serves to keep the metal ions uniformly distributed
throughout the viscous liquid, formed during evaporation but also
helps to facilitate the formation of a fluffy, voluminous, mesoporous
carbon-rich precursor material. During decomposition of these metal
ion containing precursors, nascent metal oxides forms, which are
basically small atomic clusters with proper chemical homogeneity,
imbedded in this porous carbonaceous material. These nascent metal
oxides finally produce desired single-phase α-Fe2O3 nanopowders. The
decomposition of carbonaceous material produces gases (such as CO,
CO2, NOX and water vapor) that help the precursor material to dissipate
the heat of combustion and thus inhibit the sintering of fine particles
during the process to produce nanosized oxides [10–13,19,20].

3.5. DC Resistivity Measurement

Fig. 2. X-ray diffraction spectra of (a) precursor-1, (b) precursor-2, (c- e) calcined
powders of precursor-1 at 250, 350, 450 °C respectively and (f- h) calcined powders of
precursor-2 at 250, 350, 450 °C respectively.
lay within a narrow range of 27- 30 nm and 30-35 nm for the powders
prepared from precursor-1 and precursor-2 respectively.
3.3. TEM Analysis
The variation of resistivity with change in temperature was
measured for the pellet prepared by using calcined powders prepared
from precursor 1 and 2 (calcination temperature is 450 °C) and now
onwards will be referred as sample-1 and sample-2 respectively. The
change of resistivity with temperature of these samples is shown in
Fig. 5. To prevent grain growth, we have avoided sintering at high

Average particle size of the calcined powders was measured by

using high resolution TEM and micrographs for the powder calcined at
450 °C are shown in Fig. 3 (a, b). The micrographs indicate that average
particle size of the calcined powders was in the 20-30 nm range.
Particles were uniformly elongated and formed loose aggregates.

3.4. BET Surface Area and SEM Analysis

Multiple point BET surface area measurement of all the calcined

powders exhibited a Type II physisorption isotherm with a typical H3
type hysteresis loop [17]. This indicates the formation of aggregated
particles with slit like pores. BET surface area of calcined powders,
prepared from precursor-1 and precursor-2, was found to be ~ 35 m2/
gm and ~20 m2/gm respectively and the BJH (Barret-Joyner-Halenda)
average pore diameter was about 15 nm. The data implies that the α-
Fe2O3 nanopowders as obtained could be potentially applied in
various catalytic reactions and adsorption, as in the removal of heavy
metal ions and other pollutants in water treatment [1].
Surface morphology of the calcined powder was studied using SEM
using two types of samples: (I) sample pellet prepared by using
powders calcined at 450 °C and (II) pellet prepared using the powder
calcined at 450 °C and then sintered at 1100 °C for 2 h. Calcined
powders prepared from Precursor -1 and precursor-II was used
separately to prepare pellets. The respective micrographs are shown
in Fig. 4 (a) and (b). While the calcined powder (sample I) showed
aggregation of nanoparticles, the sample sintered at high temperature
(sample II) revealed a uniformly distributed structure of the coarsened
grains. Coarsening of grains at elevated temperature was observed due
to fusion of the nanosize particles. As a result, the particle size was in
the micrometer range for the sintered sample. The particles in both
cases were found to be elongated and the shape of particles is in sync
with the hexagonal corundum structure of α-Fe2O3 [18].
TGA- DSC, XRD and TEM analysis of the synthesized precursors and
calcined powders confirmed that oxidative decomposition of pre-
cursors lead to the formation of single phase α-Fe2O3 nanopowders.
The chemical process starts from homogeneous distribution of metal
ions in solution. A fluffy mass forms due to complete evaporation the
solution, which is effectively a carbonaceous material having a porous
structure. In method -I, water-soluble metal ions are uniformly
anchored in the polymeric network structure of PVA and this possibly Fig. 3. (a, b). TEM micrograph of calcined α-Fe2O3 powder prepared from precursor-1
serves to prevent their segregation, or any intermittent precipitation (a) and precursor-2 (b).
248 P.P. Sarangi et al. / Powder Technology 192 (2009) 245–249
Fig. 4. SEM micrographs of (a) sample prepared by using calcined powder (450 °C) of precursor-1, (b) sample prepared by using calcined powder (450 °C) of precursor-1 and then sintered
at 1100 °C, (c) sample prepared by using calcined powder (450 °C) of precursor-2, (d) sample prepared by using calcined powder (450 °C) of precursor-2 and then sintered at 1100 °C.
temperatures. Instead we have heat treated the pellet at 450 °C for
2 hours so that the nanostructure of the powder could be preserved. It
was observed that (i) sample-1 and Sample-2 showed the room
temperature resistivity at 28 °C 4.6 × 105 Ωcm, and 2.3 × 108 Ωcm
respectively, (ii) The electrical resistivity of the samples increased
with increase in temperature. Sample-1 attainted maximum value of
1.5 × 108 Ωcm at 115 °C, where as for sample-2 maximum resistivity
was 6.6 × 108 Ωcm at 85 °C (iii) further increase in temperature
resulted decrease in resistivity. In case of sample-1, it acquired a value
of 8.9 × 105 Ωcm at 225 °C. For sample 2, resistivity decreased up to
1.3 × 106 Ωcm at 225 °C. The room temperature resistivity of the
Fig. 5. Variation of electrical resistivity of the synthesized α-Fe2O3 with change in
temperature (a) sample-1 and (b) sample-2.
synthesized material is higher than that of nanocrystalline (~30 nm)
films of hematite prepared by sol-gel technique [3].
Detailed investigations on the behavior of electrical resistivity of
the synthesized α-Fe2O3 powder with the change in temperature and
the impact of sintering conditions on resistivity are in progress. There
is also an ongoing effort to understand the mechanism responsible for
the nature of the curve obtained.
4. Conclusions
Two simple chemical methodologies have been successfully devel-
oped to synthesize single phase α-Fe2O3 nanopowder at a relatively low
temperature. The synthesized powder has average particle size in the
range of ~20-30 nm and BET surface area of ~35- 20 m2/gm. The surface
area measurement indicated the presence of plate-like, aggregated
particles which is further confirmed by the observed surface morphol-
ogy. Sintering at high temperature showed a uniformly distributed
structure of coarsened grains in the micrometer scale. The high room
temperature resistivity of the samples (the order of 108 Ωcm) indicates
their potential applications in humidity and gas sensors [3,21].
The important features of the methods reported here are (i)
formation of pure phase α- Fe2O3 nanoparticles in the precursor even
without calcinations for method 2, (ii) comparatively low calcinations
temperature is required for the preparation of nanopowders, (iii) no
impurity phase forms during any stage of processing, (iv) use of simple
and cheap starting materials and water as solvent, instead of costly
metal complex compounds or delicate reagents or organic solvents, help
in reducing the cost of the product, (v) not only these methods are cost-
effective but also less time-consuming. In all, the simplicity of these
methods to produce nanostructured, pure α-Fe2O3 powder makes them
attractive as compared to other reported synthetic methods.
 P.P. Sarangi et al. / Powder Technology 192 (2009) 245–249
Acknowledgement
The authors gratefully acknowledge financial support from DRDO
(Project no: EPIR/ER/0605042/M/01/929) and DST (Project no: SR/
S1/IC-39/2006), India. We also express our thanks to Prof. T. K.
Chandrasekhar and Dr.V.S. Prasad, NIIST, Thiruvananthpuram, India
and Dr. Rahul Mohan, NCAOR, Goa, India for recording TEM and SEM
micrographs respectively.
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