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Physica B 390 (2007) 2327

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Preparation of a-Fe2O3 nanoparticles by high-energy ball milling

Li-Li Wang, Ji-Sen Jiang
Department of Physics, Center of Functional Nanomaterials and Devices, East China Normal University, Shanghai 200062, PR China
Received 8 May 2006; received in revised form 14 July 2006; accepted 19 July 2006

Abstract

a-Fe2O3 nanoparticles were prepared by high-energy ball milling using a-FeOOH as raw materials. The prepared samples were
characterized by transmission electron microscopy (TEM), Mossbauer spectroscopy, X-ray diffraction (XRD) and differential thermal
analysisthermogravimetric analysis (DTATGA). The results showed that after 90 h milling a-Fe2O3 nanoparticles were obtained, and
the particle size is about 20 nm. The mechanism of reaction during milling is supposed that the initial a-FeOOH powder turned smaller
and smaller by the high-speed collision during ball milling, later these particles turned to be superparamagnetic, at last these
superparamagnetic a-FeOOH particles were dehydrated and transformed into a-Fe2O3.
r 2006 Elsevier B.V. All rights reserved.

PACS: 78.67.Bf; 76.80.+y; 78.30.Hv

Keywords: High-energy ball milling; Nanomaterials; a-FeOOH; a-Fe2O3; Mossbauer spectroscopy

1. Introduction
a-Fe2O3 (hematite) is not only a strategic industrial
material, but also one of the most used metal oxides with
various applications in many scientic and industrial elds.
It is one of the most frequently used catalysts in chemical
industry [1] and a potential candidate as a photoanode for
possible photoelectrochemical cells [2]. Moreover, a-Fe2O3
can be used as gas sensor material to detect the combustible
gases such as CH4, C3H8 and i-C4H8 [3,4]. There are many
kinds of methods to prepare a-Fe2O3 nanoparticles, e.g.
hydrothermal reaction [57], microwave [8], solgel method
[9], microemulsion method [10], forced hydrolysis [11] and
solid-phase grinding [12].
High-energy ball milling is an important way to produce
nanoparticles. It has many advantages, e.g. low cost,
simple operation, high yield and so on. At the same time,
the inuence of ball milling on the phase transition and
reaction of inorganic nonmetal materials is an interesting
topic for researchers. Randrianantoandro et al. [13] studied
the direct phase transition of a-Fe2O3 to g-Fe2O3. Uehara
et al. [14] studied the structure changes of iron oxide in
Corresponding author.
E-mail address: jsjiang@phy.ecnu.edu.cn (J.-S. Jiang).
different media by ball milling. Sanchez et al. [15] and Lee
et al. [16] found that a-Fe2O3 could be produced by ball
milling g-Fe2O3. Jiang et al. [17] prepared 10 nm a-Fe2O3
nanoparticles directly from crude a-Fe2O3 by high-energy
ball milling, and found that the surface anisotropy constant
of a-Fe2O3 nanoparticles produced by this method is
higher than bulk material. Gonzalez et al. [18] studied the
structure and phase changes of a-FeOOH during ball
milling mainly by XRD.
In this report, a-FeOOH was milled in air at room
temperature, and the resultant particles, the phase change
and the reaction mechanism of a-FeOOH during ball
milling were mainly analyzed by Mossbauer spectroscopy
as well as by TEM, XRD and DTATGA.
2. Experimental
For the milling experiment, 10 g of goethite powder (a-
FeOOH, yellow powder) was used. High-energy ball
milling was carried out in a planetary ball mill. The milling
was performed in a closed container with a hardened-steel
vial of 100 ml volume and 100 hardened-steel balls of a
diameter of 8 mm at ambient temperature in air without
any additives. The milling intensity was 200 rpm and the

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doi:10.1016/j.physb.2006.07.043
 ARTICLE IN PRESS
24 L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 2327
ball-to-powder weight ratio of 20:1 was chosen. After
selected milling times, the mill was stopped and a small
amount of powder was taken from vial for measurement.
The milling lasted for 90 h in all.
The 57Fe Mossbauer spectra were obtained from
powdered samples in the transmission mode with the
57
Co in Cr matrix as the source moving in constant-
acceleration regime. Hyperne interaction parameters were
derived from the Mossbauer spectra using a least-squares
method. The spectrometer was calibrated using a standard
25 mm a-Fe foil. For low-temperature measurement, liquid
nitrogen was used. XRD were performed on a diffract-
ometer manufactured by Rigaku with Cu Ka radiation
(l 0.15406 nm) in the range of 2y 10801 by a step of
0.021. TEM observations were carried out using a JEM-
100CX at 200 kV. DTATGA analyses were obtained in a
TGA/SDTA851e manufactured by METTLER in nitrogen
atmosphere and with a heating rate 10 K/min.
3. Results and discussion
3.1. Characterization of the structure and morphology of
nanoparticles
Fig. 1 (a) is an X-ray diffraction pattern of the initial
powders. The diffraction pattern is consistent with a-
FeOOH (JCPDs card 29713). Therefore, a-FeOOH is the
main component of the initial powders. Fig. 1 (b) is an X-
ray diffraction pattern of the sample milled for 90 h. The
diffraction pattern of the sample is consistent with a-Fe2O3
(JCPDs card 13534). This means during the milling
process the mechanochemical reaction occurred, i.e. after
milled for 90 h a-FeOOH transformed into a-Fe2O3.
Fig. 1. XRD of initial powder (a) and sample milled for 90 h (b).
a-Fe2O3 was synthesized through the following reaction:
2aFeOOH ! a2 O3 H2 O: (1)
The particle size of the prepared sample (milled for 90 h)
is about 20 nm by Sherrers formula.
The TEM image of sample milled for 90 h (Fig. 2) shows
the morphology of particles is nearly spherical. The particle
size from the picture is about 18 nm, which is consistent
with the result by XRD.
3.2. Analysis of milling process
Some selected Mossbauer spectra recorded at 300 K are
presented in Fig. 3. A set of asymmetrically broadened
sextet presents in the spectrum of the sample before milling
(0 h). The tting parameters are shown in Table 1.
According to the value of hyperne eld [19] and the
shape of the spectrum [20], sextets 25 (Table 1) are
attributed to a-FeOOH. Another small sextet with
506.62 kOe hyperne eld (sextet 1 in Table 1) is also
presented in the spectrum of raw material. This sextet is
estimated to be a-Fe2O3 from the value of hyperne eld
[19]. From the analysis above we conclude that the initial
powder consists of a-FeOOH mostly and a trie a-Fe2O3.
It shows in Fig. 3 that as the milling time prolongs, the
sextet area for a-Fe2O3 becomes larger, and the area for a-
FeOOH becomes smaller. These changes indicate that the
content of a-Fe2O3 becomes larger and the content of a-
FeOOH becomes smaller as the milling time prolongs.
Meanwhile, there are obvious doublets in the spectra of
samples milling for 3, 5 and 10 h, and the doublet in
spectrum of sample milled for 10 h is the biggest. The
doublet and the sextet for a-FeOOH both have disappeared
from the spectrum of sample of milled for 90 h (Fig. 3),
which indicates the completeness of the reaction.
The analysis can also be supported by the hyperne eld
distribution of samples milled for different time. Fig. 4 is
the hyperne eld distribution of samples corresponding to
Fig. 3. The peaks around 500 and 370 kOe represent a-
Fe2O3 and a-FeOOH, respectively. Besides, the peaks with
small hyperne eld values about 30 kOe represent doub-
lets. Fig. 5 shows the area changes of hyperne eld peaks
of doublet, sextet for FeOOH and sextet for a-Fe2O3 with
different milling time. This picture also illustrates that the
longer the milling time is, the more intensive the peak
representing for a-Fe2O3 is, and the weaker the peak
representing for a-FeOOH is. The intensity of doublet
increases before 10 h and then decreases.
Samples milled for 3, 5 and 10 h all have obvious
doublet. It can help us understand the mechanism of
mechanochemical reaction to analyze the corresponding
substance of the doublet. The sample milled for 10 h that
has the biggest doublet is chosen. There are visual peaks of
a-Fe2O3 (peaks with crosses in Fig. 6) in the XRD pattern
of this sample, which indicates that part of a-FeOOH has
transformed into a-Fe2O3. Fig. 7 is the Mossbauer spectra
of this sample at room temperature (300 K) and liquid
 ARTICLE IN PRESS
L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 2327 25

Fig. 2. TEM photo of sample milled for 90 h.

Fig. 4. Hyperne eld distribution of different samples.

nitrogen temperature (77 K). Table 2 shows the parameters

Fig. 3. Mossbauer spectra of different samples at room temperature. of the Mossbauer spectra. The spectrum at 77 K is
completely composed of magnetic sextets. The areas of
the sextets with the largest hyperne eld representing for
Table 1
a-Fe2O3, both at 300 and 77 K, are nearly the same, which
Parameters of Mossbauer spectra of raw material indicates the doublet at room temperature is mainly due to
superparamagnetic particles of a-FeOOH. From the
Hyperne I.S (mm/s) QS (mm/s) Area hyperne eld distribution of the sample at room
eld (kOe)
temperature and 77 K (Fig. 8), we can draw the same
Sextet 1 506.62 0.81 1.00 0.030 conclusion. From the distribution curve of hyperne eld
Sextet 2 372.65 0.37 0.26 0.245 of the sample at low temperature (77 K), we can also see
Sextet 3 347.10 0.37 0.26 0.440 that the doublet has disappeared. The hyperne eld value
Sextet 4 311.23 0.37 0.27 0.086
of a-Fe2O3 at low temperature is a little larger than that at
Sextet 5 279.82 0.41 0.19 0.199
room temperature, while the value of FeOOH at low
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26 L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 2327

Table 2
Parameters of Mossbauer spectra at 300 and 77 K of the sample milled for
10 h

Temperature Hyperne IS (mm/s) QS (mm/s) Area

eld (kOe)

300 K Doublet 0.31 0.82 0.237

Sextet 1 456.74 0.33 0.15 0.148
Sextet 2 371.30 0.31 0.25 0.080
Sextet 3 343.69 0.32 0.24 0.064
Sextet 4 289.19 0.29 0.14 0.471
77 K Sextet 1 495.51 0.39 0.10 0.141
Sextet 2 435.90 0.44 0.12 0.601
Sextet 3 431.46 0.29 0.58 0.081
Sextet 4 349.98 0.31 0.41 0.176

Fig. 5. The area changes of hyperne eld peaks of doublet, sextet for
FeOOH and sextet for a-Fe2O3 with differrent milling time.

Fig. 8. Hyperne eld distribution of the sample milled for 10 h at room

and low temperature.

Fig. 6. XRD of the sample milled for 10 h. The peaks with crosses are the
diffraction peaks of a-Fe2O3.
Fig. 7. Mossbauer spectra at 300 and 77 K of the sample milled for 10 h.
temperature is much larger than that at room temperature.
It is reasonable, for the standard hyperne eld values of a-
FeOOH and a-Fe2O3 at 77 K are both larger than those at
300 K, respectively. The standard hyperne eld values of
a-FeOOH and a-Fe2O3 at 300 K are about 377 and
514 kOe, respectively, and at 77 K are about 509 and
535 kOe, respectively [19]. In the sample milled for 10 h, the
hyperne eld values of a-FeOOH and a-Fe2O3 at 300 K
are 371 and 456 kOe, respectively, and at 77 K the values
shift to 435 and 495 kOe, respectively. The area ratio of
hyperne eld of a-FeOOH to a-Fe2O3 is 0.86:0.14 after
normalization at low temperature. And the area ratio of
peaks of doublet: sexteta-FeOOH: sextetaFe2 O3 in Fig. 8 is
0.24:0.61:0.15 after normalization. The area of a-Fe2O3
peak hardly changed as the temperature changed from
room temperature to liquid nitrogen temperature. Only the
areas of doublet and sexteta-FeOOH changed. So we estimate
that the main substance of doublet at room temperature is
due to superparamagnetic particles of a-FeOOH. The
mechanism of mechanochemical reaction during milling

L.-L. Wang, J.-S. Jiang / Physica B 390 (2007) 2327
1.00
TGA
0.96
WL(%)
0.92
0.88
0.84
0 200 400 600
5
0 SDTA
-5
T
-10
-15
-20
0 200 400 600
Tempreture(C)
Fig. 9. TGADTA curves of samples milled for 0, 10 and 90 h.
can be supposed that the initial a-FeOOH powder turned
smaller and smaller by the high-speed collision during ball
milling, later these particles turned to be superparamag-
netic; at last these superparamagnetic a-FeOOH particles
were dehydrated and transformed into a-Fe2O3.
Fig. 9 is DTATGA curves of the samples milled for 0,
10 and 90 h. There is a weight loss possessing 2.3% of total
weight between 50 and 120 1C in the TGA curve of sample
milled for 0 h. This weight loss is due to the evaporation of
water in the sample absorbed from the air. Another weight
loss possessing 11.4% of total weight appears between 120
and 350 1C. The largest weight loss ratio is at the
temperature around 265 1C. An endothermal peak appears
in the corresponding region in DTA curve, and this peak is
attributed to the decomposition of a-FeOOH during
heating. According to Eq. (1), when a-FeOOH decomposes
to a-Fe2O3, 10% weight will lose. The weight loss value
here is close to the theoretic value. There are also two
weight loss regions for the sample milled for 10 h. The rst
weight loss region is also due to the loss of water. The
amount of weight loss is larger in the sample milled for 10 h
than in raw material for water is created in the reaction
during ball milling. The loss amount in the second weight
loss region is 8.6%, which corresponds to the decomposi-
tion of a-FeOOH remaining in the sample. We can deduce
from the loss amount that 15.2% a-FeOOH have
conversed to a-Fe2O3 after milling for 10 h. This result is
consistent with that got from Mossbauer spectrum. Only
water loss can be seen in the TGA curve of sample milled
for 90 h. There is no weight loss between 120 and 350 1C,
ARTICLE IN PRESS
27
0h and no presents in this region in DTA curve. So sample
10h
milled for 90 h is completely composed of a-Fe2O3.
90h
4. Conclusions
The experiment shows that the structure of a-FeOOH
800 can be changed by high-energy ball milling. Using
Mossbauer spectroscopy, TEM, XRD and TGADTA,
we know that the initial a-FeOOH powder turned smaller
and smaller by the high-speed collision during ball milling,
later these particles turned to be superparamagnetic, at last
these superparamagnetic a-FeOOH particles were dehy-
drated and turned into a-Fe2O3. The resultant is a-Fe2O3
nanoparticles with 20 nm in size after a certain milling time.
800
Acknowledgments
This work was supported by Shanghai Nanotechnology
Promotion Center (0352 nm113).
References
[1] N. Mimura, I. Takahara, M. Ando, Catal. Today 45 (1998) 61.
[2] I. Cesar, A. Kay, J.A. Gonzalez Martinez, M. Gratzel, J. Am. Chem.
Soc. 128 (2006) 4582.
[3] M. Matsuoka, Y. Nakatani, H. Ohido, Nat. Tech. Rep. 24 (1978)
461.
[4] L. Huo, W. Li, L. Lu, H. Cui, S. Xi, J. Wang, B. Zhao, Y. Shen,
Z. Lu, Chem. Mater. 12 (2000) 790.
[5] X. Wang, X. Chen, X.C. Ma, H.G. Zheng, Chem. Phys. Lett. 384
(2004) 391.
[6] K. Kandori, T. Ishikawa, J. Colloid Interface Sci. 272 (2004) 246.
[7] X.H. Kang, X.Y. Wang, H.Q. Xie, L.Z. Lu, Chin. J. Mater. Res. 17
(2003) 466.
[8] Y.Z. Tang, W.M. Zhang, Chem. Res. Appl. 10 (1998) 419.
[9] K. Woo, H.J. Lee, J. Magn. Magn. Mater. 272276 (2004) e1155.
[10] A. Garcia, M. Llusar, S. Sorli, J. Calbo, M.A. Tena, G. Monros,
J. Eur. Ceram. Soc. 23 (2003) 1829.
[11] J.S. Jiang, X.L. Yang, L.W. Chen, N.F. Zhou, Appl. Phys. A 45
(1988) 245.
[12] C.X. Qiu, J.S. Jiang, Z.J. Zhao, X.L. Yang, J. Inorg. Mater. 16 (2001)
957.
[13] N. Randrianantoandro, A.M. Mercier, M. Hervieu, J.M. Greneche,
Mater. Lett. 47 (2001) 150.
[14] Y. Uehara, Bull. Chem. Soc. Jpn. 48 (II) (1975) 3383.
[15] R.M. Torres Sanchez, J. Mater. Sci. Lett. 15 (1996) 461.
[16] J.S. Lee, C.S. Lee, S.T. Oh, J.G. Kim, Scr. Mater. 44 (2001) 2023.
[17] J.S. Jiang, L. Gao, X.L. Yang, J.K. Guo, Acta Phys. Chim. Sinica 16
(2000) 312.
[18] G. Gonzalez, A. Sagarzazu, R. Villalba, Mater. Res. Bull. 35 (2000)
2295.
[19] R.Z. Ma, Mossbauer, Spectroscopy Manual, Metallurgical Industry
Press, 1993, p. 362.
[20] Z. Li, Y.P. Ying, Mineral Mossbauer, Spectroscopy, Science Press,
1996, p. 133.