Journal of Alloys and Compounds 492 (2010) 585–589

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jallcom

Production and characterization of the nanostructured hollow

iron oxide spheres and nanoparticles by aerosol route
Sebahattin Gurmen ∗ , Burcak Ebin
Metallurgical & Materials Eng. Dept., Istanbul Technical University, 34469 Istanbul, Turkey

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

Article history: Nanoshell hollow iron oxide (␣-Fe2 O3 ) spheres and nanoparticles were produced by ultrasonic spray
Received 7 July 2009 pyrolysis (USP) method from iron(III) chloride salts. Iron oxide nanostructures were obtained by thermal
Received in revised form decomposition of aerosol formed in the ultrasonic generator from aqueous solution of FeCl3 as a precur-
23 November 2009
sor. Hollow structure of iron oxide particles was controlled by reaction temperature changing between
Accepted 28 November 2009
600 and 200 ◦ C and with the addition of the polyethylene glycol (PEG) iron oxide nanoparticles were
Available online 3 December 2009
fabricated. X-ray diffraction (XRD) studies and Scherrer crystalline size calculations show that the crystal
sizes of the nanostructured iron oxide were between 33 and 18 nm. Energy dispersive spectroscopy (EDS)
Keywords:
Hollow spheres
was performed to determine the chemical composition of the particles. Scanning electron microscope
Nanoparticles (SEM) investigation gave detailed information about particle size and morphology. Transmission electron
Iron oxide microscope (TEM) was used to confirm the hollow structure of the particles and identify the thickness of
Aerosol the shell.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction Several various methods have been reported to synthesize iron

oxide nanostructures by solvothermal reactions [6], template route
Nanomaterials have attracted growing attention because of [7,9], hydrothermal approach [12,13], mechanical milling [17], mild
their size dependent novel magnetic, optical, electrical, and other oxidation of micelle [18], sol–gel reactions [11,20], pyrolysis meth-
physicochemical properties that give an opportunity to use them ods [21] and microwave processes [22]. Among them, ultrasonic
various significant potential applications [1–4]. Recently, it is real- spray pyrolysis (USP) method is capable for the preparation of
ized that functionality and features of the nanostructures can be metallic and metal oxide nanostructures in various morphologies.
controlled by not only their size but also the shape of nanomateri- USP method is based on thermal decomposition or reduction of
als, so the production of nanostructures with desired morphology, constant sized aerosol droplets of the precursor solution obtained
orientation and dimensionality is also a currently a major focus by powerful ultrasound source [23–25].
for development of nanoscience and nanotechnology [5–8]. As an ␣-Fe2 O3 nanostructures can be obtained in various morpholo-
important metal oxide, hematite ␣-Fe2 O3 exhibits some important gies such as spheres, spindles, disk, polyhedral, cubes, ellipsoids,
features such as high corrosion resistance, low cost, non-toxicity flowers and flutelike [10–22]. However attempts on the production
and environmental compatibility, as well as its remarkable opti- of hollow ␣-Fe2 O3 nanostructures have increased during the last
cal, electrical and magnetic properties [8–14]. Such characteristics few years due to their promising properties which can be applied
allow the size and shape controlled ␣-Fe2 O3 nanoparticles to in useful applications [5]. On the other hand, there are still a few
possess valuable applications such as new generation of optics, pig- studies to understand possible production techniques reported
ments, catalysts, magnetic recording media, anticorrosive agents, in the literature on the production of hollow ␣-Fe2 O3 particles.
and gas sensors [7–17]. Besides the conventional applications, Tang and co-workers [5] synthesized ␣-Fe2 O3 hollow spindles
hematite particles are suitable candidates as a cathode material for and microspheres without employing templates or matrices by
rechargeable lithium-ion batteries instead of cobalt oxide based using simple hydrothermal reaction and sequential calcinations.
electrodes, which have high cost and toxicity [5,10,18]. Hollow Wang and co-workers [7] also obtained uniform hollow hematite
hematite particles might also be used as a drug delivery vehicle by spheres with diameter of about 600–700 nm and shell thickness
encapsulation of various guest molecules and this is an uncommon lower than 100 nm by direct hydrothermal treatment process.
application in biotechnology [5,19]. Bang and Suslick [26] reported that nanosized hollow hematite
particles were fabricated by ultrasound based sonochemical
method. Their stepwise process began with preparation of carbon
∗ Corresponding author. Tel.: +90 212 285 68 62; fax: +90 212 285 34 27. nanoparticles and continues with formation of Fe/carbon compos-
E-mail address: [email protected] (S. Gurmen). ite semiproducts which occurred by the help of ultrasound and at

0925-8388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2009.11.186
586 S. Gurmen, B. Ebin / Journal of Alloys and Compounds 492 (2010) 585–589

Table 1
Composition of precursor solutions, conditions of the process, and descriptions of the obtained powders (Tprecursor = 30 ◦ C, test period = 2 h, volume of used solution = 250 ml).

No. Concentration of precursor solution (mol/l) PEG content Temperature (◦ C) Flow rate of air (ml/min) Characteristic of the product

1 0.1 M (FeCl3 ·4H2 O) – 600 500 Spherical, nanostructured hollow

␣-Fe2 O3 particles
2 0.1 M (FeCl3 ·4H2 O) – 400 500 Spherical, nanostructured hollow
␣-Fe2 O3 particles
3 0.1 M (FeCl3 ·4H2 O) – 200 500 Spherical, nanostructured hollow
␣-Fe2 O3 particles and
nanoparticles
4 0.1 M (FeCl3 ·4H2 O) 5 g. 600 500 Spherical ␣-Fe2 O3 nanoparticles

Fig. 1. XRD analyses of the particles obtained from (a) PEG added FeCl3 solution at 600 ◦ C, (b) FeCl3 solution at 600 ◦ C, (c) FeCl3 solution at 400 ◦ C and (d) FeCl3 solution at
200 ◦ C reaction temperatures.

the end semiproducts were oxidized to obtain hollow particles. nanoparticles at 600 ◦ C. Very fine droplets of the aerosol were obtained in an ultra-
Nevertheless, direct production of hollow nanostructured iron sonic atomizer Gapusol 9001 (Ramine Baghai Instrumentation, with a frequency
of 2.5 MHz). The aerosol was transported by air as carrier gas via a quartz tube
oxide particles by USP method has not been studied yet.
(0.7 m length and 0.02 m diameter) to an electrical heated furnace (Nabertherm,
In this research a novel route for production of nanostructured Germany) with a temperature control of ±1 ◦ C. Under spray pyrolysis conditions in
hollow iron oxide spheres and spherical nanoparticles using FeCl3 air atmosphere and at a flow rate of 500 ml/min, the dynamic (continuous) thermal
as a precursor were investigated. The prepared nanostructures decomposition reaction took place in the quartz tube reactor (heated zone 250 mm).
were characterized by X-ray diffraction (XRD), scanning electron In order to calculate the residence time of the aerosol droplets in the furnace, vol-
ume of the reaction zone and the carried gas flow rate should be taken into account.
microscope (SEM) and transmission electron microscope (TEM). The residence time was calculated as 9.42 sec by assuming that the rate of droplets
Susceptibility of their morphology and microstructure to the pro- and the carried gas are equal. This short reaction time is sufficient for the thermal
cessing temperature and PEG addition to precursor solution was decomposition of droplets to metal oxide particle in the air atmosphere. An X-ray
determined. diffractometer (Phillips PW 1700), transmission electron microscope (JEOL 2000
EX) and scanning electron microscope (JEOL JSM 700F) were used for the charac-
terization of the obtained iron oxide nanostructures. The chemical compositions of
2. Experimental
particles were investigated by the EDS analyses. For XRD analysis, the dispersed
particles were placed on a glass substrate and allowed to dry in air at room temper-
2.1. Materials
ature. TEM images were obtained to prove the hollow structure of the particles. SEM
images were used to observe the surface morphology of particles formed at different
All the reagents (FeCl3 ·6H2 O and polyethylene glycol, PEG) were in analytical
reaction temperatures. The powders were first dispersed in ethanol and inserted in
grade and used without further purification. A water leach solution of FeCl3 ·6H2 O
ultrasonic bath for 5 min and then the suspension was dropwised onto a brass sheet
(salt powders were dissolved in deionized water) was used as starting material for
to make a thick film, which later coated by palladium for SEM characterization.
this research. The deionized water was used for all solutions. The concentration of
Table 1 contains data for chemical composition of the applied solutions, condi-
the precursor solution is 0.1 mol/l. All solutions were stirred for 20 min by using a
tions of the production process and a short description of the obtained structures.
magnetic stirrer.

2.2. Experimental procedure 3. Results and discussion

The nanostructured hollow ␣-Fe2 O3 spheres and nanoparticles were synthe- 3.1. Structure characterization
sized using the ultrasonic spray pyrolysis method. The experiments were done at
600, 400 and 200 ◦ C reaction temperatures starting from iron chloride solution with
concentration of the 0.1 mol/l for obtaining hollow iron oxide spheres. Also, PEG Fig. 1 shows representative XRD patterns of the ␣-Fe2 O3 parti-
added iron chloride with concentration of 0.1 mol/l was used to produce ␣-Fe2 O3 cles and demonstrate clearly that the crystallinity of the samples

Table 2
Crystallographic data of the samples for crystal size determination.

No. Corresponding solution Temperature (◦ C) Position 2 (◦ ) (104) FWHM (◦ ) (104) d-Spacing (Å) (104) Crystalline size (nm)

1 FeCl3 ·4H2 O + PEG 600 500 0.354 2.7016 33

2 FeCl3 ·4H2 O 600 500 0.354 2.6949 33
3 FeCl3 ·4H2 O 400 500 0.576 2.7062 18
 S. Gurmen, B. Ebin / Journal of Alloys and Compounds 492 (2010) 585–589 587

Fig. 2. EDS analyses of the particles obtained from FeCl3 solution at (a) 600 ◦ C, (b) 400 ◦ C, (c) 200 ◦ C reaction temperatures and (d) PEG added FeCl3 solution at 600 ◦ C reaction
temperature.

Fig. 3. SEM analyses of the particles obtained from FeCl3 solution at reaction temperatures (a) 600 ◦ C, (b) zoomed scale of 600 ◦ C, (c) 400 ◦ C, (d) zoomed scale of 400 ◦ C, (e)
200 ◦ C and (f) zoomed scale of 200 ◦ C.
588 S. Gurmen, B. Ebin / Journal of Alloys and Compounds 492 (2010) 585–589

produced at 600 ◦ C are higher than the samples obtained at 400

and 200 ◦ C. All of the diffraction peaks for Fig. 1a and b can be
indexed to rhombohedral phase ␣-Fe2 O3 with lattice parameters
a = 5.034, c = 13.75 Å (Space Group: R3̄c), which are consistent with
the reported data (JCPDS Card No: 079-1741). XRD pattern of parti-
cles obtained at 400 ◦ C just only shows two main peaks of ␣-Fe2 O3
(Fig. 1c). Moreover, particles prepared at 200 ◦ C exhibit amorphous
phase (Fig. 1d).
Crystalline size calculated from XRD patterns by using Scherrer
Equation,
K
t= (1)
Bcos
defines a simple relationship between crystalline size and peak
width. In this equation K is constant which value is between 0.85
and 0.9,  is the wavelength of the X-ray (CuK␣1 = 1,5418 Å), B is the
full width high maximum, FWHM (in radians) of the peak due to
size effect,  is the Bragg angle, and t is the particle size [17,24]. The
(1 0 4) peak in the Fig. 1 was used for the crystalline size determina-
tion by Scherrer formula and instrumental broadening was taken
into account for all calculations to determine accurate crystal sizes.
Table 2 contains crystallographic data for crystal size determina-
tion of the samples obtained at different conditions. Crystal sizes
of the particles, obtained using FeCl3 aqueous solution and PEG
added same solution at 600 ◦ C, are 33 nm. Decreasing of the reac-
tion temperature to 400 ◦ C causes the reducing in the crystal size
to 18 nm.
The compositions of the products prepared by USP method were
further studied by EDS. Fe and O elements are clearly observed
from the EDS images, which were shown in Fig. 2, indicating a com-
plex composition of the products. Besides that EDS results denote
that the weight ratios of Fe to O are close to 69:31 for all samples
which agree well with the calculated value from the formula of the
hematite.
Both of the XRD and EDS results proof that ␣-Fe2 O3 structures
were obtained from FeCl3 solution in the absence of PEG in 400 and
600 ◦ C temperatures. Otherwise, products synthesized from FeCl3
solution in the absence of PEG at 200 ◦ C shows an amorphous phase
but have the same Fe:O weight ratio with hematite. Moreover, used
PEG in the solution has not reducing effect on Fe2 O3 obtained from
decomposition of FeCl3 in this reaction system because it is more
possible that carbon and hydrogen in the PEG reacted with free
oxygen in the air at 600 ◦ C, and also ferric (iron(III)) captured the
oxygen to form Fe2 O3 from air.

3.2. Morphological characterization of hollow spheres

Fig. 4. TEM micrographs of the particles obtained from FeCl3 solution at (a) 600 ◦ C,
(b) 400 ◦ C and (c) 200 ◦ C reaction temperatures.
The morphology of the prepared hollow ␣-Fe2 O3 spheres was
characterized by SEM and TEM. Fig. 3 shows the SEM images of
␣-Fe2 O3 particles obtained by USP method using FeCl3 aqueous thickness of the hollow iron oxide particles about 50 nm, can be
solution at 600, 400 and 200 ◦ C. It is obviously seen from the Fig. 3, seen obviously in Fig. 4b. Dispersed nanoparticles less than 30 nm
all ␣-Fe2 O3 particles are submicron size in spherical morphol- size can be observed in Fig. 4c. These micrographs indicate that
ogy. Magnified SEM image of ␣-Fe2 O3 particles obtained at 600 ◦ C sizes of the crystallites are nearly same by calculated values using
(Fig. 3b) indicates that these submicron particles are the aggre- Scherrer formulation. So, it is obviously seen that TEM observation
gates of nearly 30 nm-sized nanoparticles. The holes, which formed supported and confirmed the determined crystal size by the XRD
due to insufficient sintering at 400 ◦ C reaction temperature, can results.
be observed clearly in Fig. 3c and d on the surface of the parti-
cles. Also, Fig. 3d exhibits those very fine nanoparticles with the 3.3. Morphological characterization of nanoparticles
range of 20–25 nm that generate submicron particles by aggrega-
tion. Exposed surface holes and nanosize shell structures of the PEG added aqueous solution of FeCl3 was used to produce
particles obtained at 200 ◦ C were detected in Fig. 3e and f. ␣-Fe2 O3 nanoparticles by USP method. SEM images of the nanopar-
TEM bright field micrographs of the samples obtained from ticles are given in Fig. 5. The shape of ␣-Fe2 O3 nanoparticles
FeCl3 aqueous solution at 600, 400 and 200 ◦ C are shown in Fig. 4. is nearly spherical with homogeneous size distribution (Fig. 5a).
TEM micrographs is given in Fig. 4a represents the hollow ␣-Fe2 O3 Nanoparticles with the diameters about 30 nm were prepared using
spheres about 100 nm shell thickness produced at 600 ◦ C. Decreas- PEG added precursor, as shown in Fig. 5b. SEM results indicate that
ing of the thermal decomposition temperature reduces the shell aggregation of the primary nucleated ␣-Fe2 O3 particles by sintering
 S. Gurmen, B. Ebin / Journal of Alloys and Compounds 492 (2010) 585–589 589

Also, ␣-Fe2 O3 nanoparticles were fabricated by ultrasonic spray

pyrolysis method from PEG added 0.1 M FeCl3 aqueous solution at
600 ◦ C under 500 ml/min air volumetric flow rate. The X-ray analy-
sis of the particles indicate the rhombohedral crystalline structured
␣-Fe2 O3 with 33 and 18 nm crystal sizes fabricated at high reac-
tion temperature conditions, respectively 600 and 400 ◦ C. Besides
that, ␣-Fe2 O3 particles with amorphous phase were obtained at
low temperature. SEM images show that hollow ␣-Fe2 O3 spheres
were formed by the aggregation of nearly 30 nm-sized nanoparti-
cles. TEM results verified the hollow structure and confirmed that
reducing the reaction temperature from 600 ◦ C to 400 ◦ C decreases
the shell thickness of the ␣-Fe2 O3 hollow spheres. Moreover, it is
stated that PEG addition in corresponding solution prevents the
aggregation of nanoparticles and makes the production of ␣-Fe2 O3
nanoparticles possible.

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