Journal of Alloys and Compounds 326 (2001) 292–297 L

www.elsevier.com / locate / jallcom

¨
Nanophase iron oxides by ball-mill grinding and their Mossbauer
characterization
a b b ,1 a c b,
S. Bid , A. Banerjee , S. Kumar , S.K. Pradhan , Udayan De , D. Banerjee *
a
Department of Physics, University of Burdwan, Golapbag, Burdwan 713104, W. Bengal, India
b
Department of Physics, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009, India
c
Variable Energy Cyclotron Center, Department of Atomic Energy, 1 /AF Bidhan Nagar, Calcutta 700064, India
Received 3 July 2000; received in revised form 27 November 2000; accepted 20 December 2000

Abstract

Ball-mill grinding of ferric oxide, Fe 2 O 3, to obtain nanophase samples has been undertaken for different duration with repeated X-ray
diffraction monitoring of nanophase formation. Particle size and strain have been calculated from XRD patterns, for different periods of
¨
ballmilling at 300 rpm. Mossbauer spectra of as-supplied or bulk iron oxides and these finely ballmilled samples have been compared
looking for the signature of superparamagnetism possible in the nanophase samples.  2001 Elsevier Science B.V. All rights reserved.

¨
Keywords: Ball-milling; a-Fe 2 O 3 ; Nanophase; X-ray diffraction; Mossbauer spectra

1. Introduction erties of nanophase materials have been investigated by

In recent years nanocrystalline materials have been
extensively investigated due to their unusual properties and
application potentials [1]. The iron oxides, a-Fe 2 O 3
(hematite) and Fe 3 O 4 (magnetite), for example, are im-
¨
portant as electrical and magnetic materials. Mossbauer
spectra [2] of fine particles of a-Fe 2 O 3 , produced by a
chemical impregnation process and supported on a high
area silica, in different sizes, have been recorded before the
name nanophase was coined. Among various methods of
producing nanomaterials, ball-milling [3] has potential for
large scale production and is being further developed.
Particle size reduction and possible chemical transforma-
tion of the sample during ball-milling are believed to be
influenced by ball-to-powder mass ratio (BPMR), milling
time, milling environment, milling speed as well as the
type of ball-mill itself. Recently, Zdujic et al. [4] reported
the results of ball-milling of a-Fe 2 O 3 powder in air and in
closed atmosphere milling conditions using a planetary
ball-mill, and showed the results to be very sensitive to
milling conditions. Recently, structural and magnetic prop-
*Corresponding author. Fax: 191-33-351-9755.
E-mail address: dbanerji@cubmb.ernet.in (D. Banerjee).
1
Presently at JIS College of Engineering, Kalyani 741235, India.
X-ray powder diffraction [1,5,6,14] and Mossbauer ¨
spectroscopic [1,7–9] techniques. The present work is
devoted to X-ray powder diffraction line profile analysis
¨
and Mossbauer studies on differently ball-milled a-Fe 2 O 3
¨
fine particles. It is noted that the nature of the Mossbauer
spectrum depends on the relation between the time of
measurement and that of the magnetization vector relaxa-
tion. If the time of observation is much less than the
relaxation time, the particles exhibit ferromagnetism, while
in the opposite case one observes superparamagnetism.
Also, the relaxation time of superparamagnetic particles
increases with particle volume, as detailed later. Therefore,
in ferromagnetic samples consisting mainly of nanoparti-
¨
cles, the Mossbauer spectrum is usually a superposition of
a superparamagnetic doublet, corresponding to particles of
smaller size, and a Zeeman sextet, corresponding to large
ferromagnetic particles [10,11].
2. Sample preparation and experiments
Analytical-grade a-Fe 2 O 3 powder was used as the
starting material for milling in Fritsch Pulverisette 5
planetary ball-mill. Two hardened-steel vials of 80 cm 3
volume, each charged with 30 hardened-steel balls of 10
mm diameter were used for milling, keeping the angular
velocity of the supporting disc at 31.42 rad s 21 (300 rpm).

0925-8388 / 01 / $ – see front matter  2001 Elsevier Science B.V. All rights reserved.
PII: S0925-8388( 01 )01287-7
 S. Bid et al. / Journal of Alloys and Compounds 326 (2001) 292 – 297
The powder was milled in air atmosphere without any
additives (dry milling) under ‘closed’ milling conditions,
i.e., the vials were not opened during all the milling
periods. Milling with the ball-to-powder mass ratios
(BPMR) of 30:1 and 35:1 have been tried.
The X-ray powder diffraction (XRD) stepscan data
(2u 50.028) were collected on a Philips PW 1710 auto-
¨
matic diffractometer with Cu Ka radiation. The Mossbauer
spectra have been recorded in transmission geometry using
¨
a constant acceleration type. Mossbauer spectrometer with
a 5 mCi Co 57 source in a Pd matrix. A Xe-filled proportion
counter has been used as detector. The data have been
acquired in the MCS mode in a multichannel analyzer.
¨
Mossbauer spectra of Fe 2 O 3 fine particles produced by
ball-milling have been recorded at room temperature.
3. Results and discussions
We have considered the most prominent reflections of
a-Fe 2 O 3 (012), (104), (110), (113), (024), (116), (214)
and (030) for X-ray line profile analyses (XRLPA). The
very weak and / or overlapping reflections from Fe 3 O 4 and
Fe ( 12x) O x , that appears to have been formed due to
milling, have not been considered for XRLPA. As some of
the peaks of a-Fe 2 O 3 are partially overlapping (Fig. 1), it
is of prime necessity to estimate the correct background of
Fig. 1. X-ray powder diffraction patterns for different periods of ball-milling of Fe 2 O 3 .
293
the X-ray spectra in the vicinity of overlapping region in
order to obtain the accurate values of peak-position
maxima, peak intensities, full-width at half-maxima
(FWHM) and Gaussianity of the experimental profiles.
The Scherrer equation [12] for grain size (D) estimation
or Warren–Averbach method of Fourier analysis of the line
shapes [12] for determination of particle size (De ) and
r.m.s. strain k´ 2 l 1 / 2 have been used after the correction for
background by a standard profile fitting procedure [13].
For peak fitting, the most suited pseudo-Voigt peak shape
function has been used, as recommended by Young and
Wiles [14]. The said function has the following refinable
parameters: peak-height (I), peak area (S), peak maximum
position (2umax ), full width at half maxima (FWHM), an
asymmetry parameter (A), Gaussiabity of the peak (G) and
background parameters (linear / non-linear). Two weighting
schemes can be used during the profile fitting: (a) un-
weighted refinement (w I 51) and (b) weight equals to the
reciprocal of the standard deviation. Refinement uses the
Marquardt minimization algorithm. The adopted software
[13] allows simultaneous fittings of up to 15 overlapping
peaks of mixed Gaussian and Lorentzian type. For both the
Scherrer and Warren–Averbach analyses and a specially
prepared polycrystalline Si is used as the ‘instrumental
standard’ [15]. The results of X-ray powder diffraction line
profile analysis on differently ball-milled samples of Fe 2 O 3
is presented in Table 1.
294 S. Bid et al. / Journal of Alloys and Compounds 326 (2001) 292 – 297

Table 1
Results of X-ray powder diffraction line profile analysis on differently ball-milled samples with Fe 2 O 3 (0 h) denoting the as-supplied or the starting
material
Sample hkl Lattice Particle size (nm) R.m.s. strain (10 23 )
parameter
(nm) Scherrer Warren–Averbach Warren–Averbach
(D) hkl (D) av (D) hkl (D) av k´ 2 l 1hkl/ 2 k´ 2 l 1av/ 2
Fe 2 O 3 012 a50.50250 57.05 62.26 29.8 35.2 1.71 0.96
(0 h) 104 c51.36838 54.91 32.4 1.37
110 61.61 30.1 1.03
113 53.12 59.8 1.32
024 62.69 35.3 0.79
116 62.40 27.6 0.58
214 80.94 36.7 0.41
030 65.38 30.0 0.47
Fe 2 O 3 012 a50.50281 8.08 7.70 5.02 3.86 9.97 5.89
(5 h) 104 c51.37402 8.04 3.01 7.60
BPMR 110 9.56 6.54 6.16
530:1 113 6.93 3.29 6.06
024 6.85 3.20 5.09
116 7.59 3.62 4.21
214 6.74 3.00 4.25
030 7.84 3.21 3.81
Fe 2 O 3 012 a50.50320 8.16 9.12 6.16 4.46 10.38 5.19
(10 h) 104 c51.37751 10.70 4.67 4.99
BPMR 110 9.69 3.93 5.44
535:1 113 9.64 3.85 4.82
024 7.75 3.15 4.93
116 10.21 4.85 3.15
214 7.72 5.46 4.44
030 9.10 3.62 3.38
Fe 2 O 3 012 a50.5038 8.20 10.39 3.27 4.81 9.53 4.53
(15 h) 104 c51.37638 9.91 3.95 5.76
BPMR 110 10.41 5.89 5.04
535:1 113 11.66 6.41 3.79
024 10.83 4.37 3.56
116 8.87 4.25 3.61
214 12.59 5.12 2.44
030 10.72 5.26 2.58
Fe 2 O 3 012 a50.50391 10.39 9.41 5.00 4.71 6.92 4.42
(20 h) 104 c51.37664 9.27 5.17 4.94
BPMR 110 9.02 3.61 5.89
530:1 113 9.97 7.93 2.36
024 7.45 4.11 4.92
116 9.95 4.04 3.54
214 6.96 2.85 4.39
030 12.29 5.01 2.45

¨
Mossbauer spectra for all the samples (Table 2) are
fitted by least-square fitting programme [16] with Lorent-
zian profiles to determined the line positions, line-widths
and peak-intensities. The continuous lines represent the
computer fitted data, where as the dot represents the
experimental data. The isomer shift (IS), quadrupole
splitting (QS), internal hyperfine field (Hn ), obtained from
¨
best fitted Mossbauer spectra lines are presented in Table
2. Two typical spectra of bulk or as-supplied Fe 2 O 3 and 5
h ball-milled Fe 2 O 3 powder samples are shown in the Fig.
¨
2a,b, respectively. The Mossbauer spectra of different
ball-milled a-Fe 2 O 3 samples consists of a sextet and a
doublet.
¨
Mossbauer spectrum of the bulk a-Fe 2 O 3 sample,
having particle size 35.2 nm according to Warren–Aver-
bach calculations, shows a six-finger pattern having IS5
0.41 mm / s and Hn 551.82 Tesla, which is in agreement
with earlier findings [2]. Kundig and Bommel [2] have
obtained only a central doublet with samples having
particle size |18 nm or lower. They attributed the doublet
 S. Bid et al. / Journal of Alloys and Compounds 326 (2001) 292 – 297 295

Table 2
¨
Mossbauer parameters for differently ball-milled a-Fe 2 O 3
Sample IS D12 2 D56 a QS Hn FWHM, Relative
(mm / s) (mm / s) (mm / s) (Tesla) G (mm / s) intensity (%)
Fe 2 O 3 (0 h)
Six-finger 0.41 0.22 20.08 51.82 0.34 100
Doublet – – – – – 0
Single line – – – – – 0
Fe 2 O 3 (5 h)
Six-finger 0.37 0.197 0.15 49.467 – 84.09
Doublet 0.38 – 2.33 – 0.71 15.91
Fe 2 O 3 (10 h)
Six-finger 0.48 0.008 0.087 49.13 – 80.52
Doublet 0.40 – 1.79 – 2.27 19.48
Single line – – – – – 0
Fe 2 O 3 (15 h)
Six-finger 0.37 0.01 0.27 48.89 – 77.18
Doublet 0.40 – 1.69 – 1.22 22.82
Single line – – – – – 0
Fe 2 O 3 (20 h)
Six-finger 0.35 0.167 0.038 49.867 – 74.22
Doublet 0.64 – 2.33 – 1.89 25.78
Single line – – – – – 0
a
(D12 2 D56 ) is the energy difference between lines 1 and 2 of the sextet, minus the energy difference between lines 5 and 6 of the sextet (line 1 is at
¨
extreme left.) All the values of Mossbauer parameters have been calculated using a-Fe as standard.

¨
to the superparamagnetic state. In our case, Mossbauer
spectrum consisted of a sextet (predominating in intensity)
and a broad central doublet for particle sizes much smaller
¨
than 18 nm (Table 2). However, the Mossbauer spectra of
the 5-h milled sample is best fitted with a sextet, a doublet
and a single line of very weak relative intensity (0.01%).
This single line having an IS50.64 mm / s can be attributed
to Fe ( 12x) O x phase. It is interesting that the relative
intensity of the doublet increases as particle size decreases
(corresponding to longer milling time). So the doublet is
attributed to the superparamagnetic behaviour of ferromag-
netic fine particles. One still needs an explanation for the
additional presence of the sextet, that obviously indicates a
ferromagnetic ordering in the samples. Appearance of this
ferromagnetic ordering can be explained either from the
theory of superparamagnetic relaxation or from a presence
of larger particles (at least.18 nm) in high proportion.
However, XRD analysis does not detect such high propor-
tion of larger particles. Therefore the only option remain-
ing is to explain the appearance of sextet from the theory
of superparamgnetic relaxation. The superparamgnetic
relaxation time is given by
t 5 t0 exp(KV/kT )
where t0 depends only slightly on temperature and is of the
order of 10 29 –10 212 , k is Boltzmann constant, T is the
temperature, K is the magnetic anisotropic energy constant,
and V is the volume of the particle. Now the time of
relaxation t at a fixed temperature depends both on particle
volume V and anisotropy energy constant K. The nature of
¨
the Mossbauer spectrum of magnetic nano-particles de-
pends on the correlation between the time of observation
(tobs ) and that of magnetization vector relaxation (t ). For
all the samples we have obtained complex Mossbauer ¨
spectra consisting of a sextet and a doublet, implying that
t (tobs . The time of relaxation t at a fixed temperature
depends both on particle volume V and anisotropic phase
constant K. In our case particle sizes smaller than that in
the experiments of Kundig and Bommel [2], which should
lead to a predominant superparamagnetic doublet. Pre-
dominance of the sextet in our patterns can be explained
through a possible variation of the anisotropy constant K
for differently ball-milled samples presumably due to
internal strain (Table 1).
It is noted that according to the model of collective
magnetic excitations, the hyperfine magnetic field of small
magnetic particles depends on particles size and broaden-
¨
ing of the Mossbauer lines can be explained by a particle
size distribution [17,18]. The magnetic splitting in a
¨
Mossbauer spectrum of small magnetic particles is general-
ly smaller than that found in a microcrystal and if the
samples contain a broad size distribution, the magnetic
(1)
splitting of the spectra of those particles will be different.
Superposition of all these spectra give rise to asymmetric
¨
and broadened Mossbauer pattern. In the present experi-
ment, hyperfine field (Hn ) obtained for the fine particle is
|49 Tesla, that for bulk sample H is |51.8 Tesla, and the
lines are asymmetric and broadened. The reduction in Hn ,
296 S. Bid et al. / Journal of Alloys and Compounds 326 (2001) 292 – 297

¨
Fig. 2. (a) Mossbauer ¨
spectrum of bulk or as-supplied Fe 2 O 3 . (b) Mossbauer spectrum of 5 h ball-milled Fe 2 O 3 .

broadening of lines and asymmetry of line shape suggest Acknowledgements

not only a broad particle size distribution but also a
fluctuation of the magnetization vector in a direction close S. Bid thanks the West Bengal (India) State Fund
to the easy direction leading to the so-called collective Fellowship (JRF); A. Banerjee and S. Kumar thank to the
magnetic excitations. UGC, Government of India, for financial support.
 S. Bid et al. / Journal of Alloys and Compounds 326 (2001) 292 – 297
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