Milling time and temperature dependence on nanoparticles synthesized by

mechanical alloying method

R. Fajarin, fajar@mat-eng.its.ac.idH. Purwaningsih, Widyastuti, D. Susanti, and R. Kurnia Helmy

Citation: AIP Conference Proceedings 1617, 63 (2014); doi: 10.1063/1.4897105

View online: http://dx.doi.org/10.1063/1.4897105
View Table of Contents: http://aip.scitation.org/toc/apc/1617/1
Published by the American Institute of Physics
 Milling Time and Temperature Dependence on Fe2TiO5
Nanoparticles Synthesized by Mechanical Alloying Method
*
R. Fajarin , H. Purwaningsih, Widyastuti, D. Susanti, and R. Kurnia
Helmy
Material and Metallurgical Engineering, Institute of Technology Sepuluh Nopember Surabaya 60111, Indonesia
* Email: fajar@mat-eng.its.ac.id

Abstract. Fe2TiO5 is one type of titanate oxides which has MxTiyOz crystal structure. It has various kinds of
applications due to its electric and magnetic properties such as spintronics, electromagnetic devices, and gas sensor. In
this study, Fe2TiO5 nanoparticles were synthesized by simple mechanical alloying using planetary ball milling machine
with various milling times and sintering temperatures. TiO2 and Fe2O3 powders obtained from coprecipitation process
were used as starting materials. The resulted Fe2TiO5 powders were characterized by X-Ray Diffraction (XRD),
Scanning Electron Microscopy (SEM), and Vibration Sample Magnetometer (VSM) in order to observe crystal quality,
particles morphology, and magnetic properties respectively. As the milling time increases and the sintering temperature
decreases, the crystal size of Fe2TiO5 phase decreases. The smallest crystal size of the synthesized Fe2TiO5 nanoparticles
was  51 nm obtained by the milling time of 25 hours and sintering at 1100oC. The distribution of the resulted Fe2TiO5
nanoparticles was not so homogeneous due to the appearance of small amount impurities. The VSM measurements show
that a paramagnetic property was observed which should be analyzed more details on the low external magnetic fields.
Keywords: Fe2TiO5, Nanomaterials, Mechanical Alloying, Milling Time, Sintering.
PACS: 81.07.-b; 81.40.-z; 81.20.Fw; 81.20.Wk; 81.20.Ev

INTRODUCTION obtained from sol-gel method and Fe(NO3)3.9H2O and

Most of electronic devices in the last decade are
based on semiconductors. Among various oxide
semiconductors, the n-type semiconductor α-Fe2O3 has
many applications and also has been studied because
of its electric and magnetic properties. The other
advantages of this oxide are low cost production, high
corrosion resistance, non-toxic and environmentally-
friendly oxides [1]. Pure phase of α-Fe2O3 has very
low conductivity. However, this electric property of α-
Fe2O3 can be increased by incorporation addition or
doping. Improving electric properties means that it
will increase the usability as a gas sensing material [2].
Addition of TiO2 in α-Fe2O3 and vice versa has
attracted many researchers to investigate their
properties, especially in optical properties [3]. Fe2TiO5
is one of the pseudobrookite solid solution FeyTi3-yO5
which has optical, electric and magnetic properties.
This titanate oxide has many applications such as Li-
ion battery and gas sensor [4, 5]. Researches on
photoelectrochemical, spin glass properties, and gas
sensitivity of both combination TiO2-Fe2O3 and
Fe2TiO5 had been done [6, 7, 8].
Several synthesis methods have been applied in
order to obtain pure Fe2TiO5 in polycrystals (bulk
forms), nanoparticles, and thin films. Fe2TiO5 thin film
on silica glass with crystal size 40 nm could be
3rd International Conference on Theoretical and Applied Physics 2013 (ICTAP 2013)
AIP Conf. Proc. 1617, 63-66 (2014); doi: 10.1063/1.4897105
© 2014 AIP Publishing LLC 978-0-7354-1254-5/$30.00
Ti(OC3H7)4 as the raw materials [9]. Fe2TiO5
nanoparticles could also be synthesized from TiCl3,
Fe(NO3)3 .9H2O, dan NH2CONH2 as the raw materials
with hydrothermal route. The particle size range
obtained from this method was 50 – 200 nm [4].
In the present paper, the nanoparticles of Fe2TiO5
are obtained by simple mechanical mixing technique
as a synthesize method. The crystal structure,
microstructure observation and room temperature
magnetic properties are analyzed.
METHODOLOGY
Iron (II) Chloride Tetrahydride, FeCl2.4H2O, and
Titanium Oxide, TiO2 (Rutile Phase), all purchased
with analytical grade product, were used as starting
materials. Pure α-Fe2O3 powders were synthesized
from sintering process of Fe3O4 powders obtained by
precipitation method of FeCl2.4H2O. The solid
solution with weight ratio of α-Fe2O3:TiO2 = 4.7:5.3
was prepared to synthesize Fe2TiO5 nanoparticles
using Planetary ball mill Fritsch Pulverisette P-5 as
mechanical alloying method with 300 rpm of milling
speed, BRP 6:1, and various milling times for 15, 20,
and 25 hours in air atmosphere. The obtained milling
powders were compacted by pressing machine and
then sintered with various temperatures at 1100, 1200,

63
1300°C for 1 hour in air condition of Carbolite
furnace.
The powder X-Ray Diffraction (XRD) patterns
were recorded using PAN Analytical Diffractometer
with wavelength 1.54056 Å of CuKα radiation, 10 –
90o 2θ range, and scan rate 0.02o. Phase identification,
lattice parameters and crystal size were analyzed using
Search-Match software and Peak-Profile analysis. The
Scanning Electron Microscope (SEM) FEI Inspect S50
was conducted to the surface of obtained powder
samples to investigate particle morphology. Vibration
Sample Magnetometer (VSM) was used to measure
the magnetization of the samples in room temperature.
RESULTS AND DISCUSSIONS
Qualitative analysis based on XRD patterns of the
obtained powders just after milling process with
various milling times are observed four identified
phases, which are Fe2O3 (hematite), TiO2 (anatase),
Fe3O4 (magnetite) and TiO2 (rutile) with corresponded
JCPDF Number of 79-0007 at 2θ 33.19°; 21-1272 at
2θ 25.28°; 89-0950 at 2θ 30.10°; and 77-0441 at 2θ
27.38°; respectively as can be seen in Figure 1. The
formation of Fe3O4 phase after milling process is due
to reversible reaction of α-Fe2O3 to Fe3O4 during
milling process. This is related to the breaking parts of
Fe-O bonding in α-Fe2O3 and reacts with oxygen
inside the vial [10]. It is suggested that the milling
process have enough energy needed to initialize the
transformation from α-Fe2O3 to Fe3O4 phase.
FIGURE 1. XRD patterns for powders obtained after
milling process for 15, 20, and 25 hours of milling time.
Based on the peak profile analysis, the peak of
anatase phase at 2θ 25.21° decreases and it is followed
by peak broadening with increasing Full Width at Half
Maximum (FWHM) value indicating transformation to
more amorphous phase. The disappearance of anatase
peaks is realized at 37.81° and 48.06° for the milling
time more than 15 hours. The decreasing anatase
phase is followed by the increasing rutile phase for
64
sample with 20 hours of milling time. Transformation
of anatase to rutile phase during mechanical alloying
process is occurred below its transformation
temperature. This is due to the thermal energy of
collision during milling process and the crystal
defects, such as vacancy and crystal distortion that
may increase the free energy of anatase phase, thus
decrease the phase transformation temperature [11].
The diffraction peaks of Fe2O3 and TiO2 (anatase)
phases increased in their intensities and broadened in
their peak widths with increasing milling time. This
may occur because of the smaller particle size and
accumulation of microstrains after mechanical alloying
process [12]. There is no solid solution detected in the
samples after milling process, even after 25 hours
milling, indicating the milling energy is not enough to
react all elements each other to form other compounds.
XRD patterns of samples after sintering process
with various temperatures at 1100, 1200, and 1300°C
for 1 hour show that there are new diffraction peaks
increase which corresponds to the pseudobrookite
(Fe2TiO5) phase as can be seen in Figure 2. The
formation of this new phase indicates partial reaction
between iron oxides and titanium oxides. The
diffraction peaks of Fe2O3 and TiO2 (anatase)
decrease, suggesting the intermetallic diffusion take
place and the solid solution reaction is occurred to
form Fe2TiO5 phase.
This phase transformation was begun at the
temperature higher than 900oC. The diffraction peaks
of Fe2TiO5 phase increased as well as the increasing of
sintering temperature. At high temperature, Fe3O4
phase is oxidized to Fe2O3 phase and reacts with TiO2
to form Fe2TiO5 phase. As increasing thermal energy,
diffusion of Ti atoms increases and fills vacancy sites
of Fe2O3 structure, thus, it increases the diffraction
peaks of Fe2TiO5 phase as well as the crystal size.
Sintering process as a heat treatment affects the crystal
growth of Fe2TiO5 phase as shown in Figure 3. The
remaining anatase phase will transform to rutile phase
at high sintering temperature. The peaks of TiO2
(rutile) phase increased with increasing sintering
temperature showing more crystalline phase was
formed in the samples.
(a)
 (b)
XRD analysis showed that Fe2TiO5 phase had not
formed yet until the samples were sintered. For the
sintered samples, as the milling time increased, the
crystal size of Fe2TiO5 phase decreased. Figure 4
shows the effect of milling time with crystal size in the
sintered samples.
The particle morphology of sintered samples was
observed by SEM images. Figure 5 represents SEM
images of the obtained particles for sample with the
milling time for 25 hours and various sintering
temperatures for 1 hour. As increasing sintering
(c) temperature from 1100 – 1300oC, the particle size
increased. This condition was shown by disappearance
of small particles and followed by increasing size of
the larger particles. Based on these images, the particle
size distribution seemed to have no homogeneity in
shape. However, the trend of particle size was
consistent with XRD data analysis.

(a) (b)

FIGURE 2. XRD patterns for obtained powders after

sintering process with various sintering temperatures at
1100, 1200, 1300oC for 1 hour for samples with milling time
for: a) 15 hours, b) 20 hours, and c) 25 hours. 10 m 10 m
100
Sintering for 15 hours (c)
90 Sintering for 20 hours
Crystal Size (nm)

Sintering for 25 hours

80

70

60

50 10 m
40
1100 1200 1300
Sintering Temperature ( C)
o FIGURE 5. Particles morphology of the sintered samples at
(a) 1100, (b) 1200, and (c) 1300oC with milling time for 25
FIGURE 3. Sintering temperature dependence of Fe2TiO5 hours.
crystal sizes with various milling times.

100 (a) (b)

o
Sintering at 1100 C
o
90 Sintering at 1200 C
Crystal Size (nm)

o
Sintering at 1300 C
80

70

60

50 10 m 10 m
40
15 20 25
FIGURE 6. Particles morphology of the sintered samples at
Milling Time (hours) 1300oC with milling time for (a) 15 hours and (b) 20 hours.
FIGURE 4. Milling time dependence of Fe2TiO5 crystal
sizes with various sintering temperatures.

65
 The differences of particles morphology and their
distributions can be seen in Figure 6 for sintered
samples at 1300oC with milling for 15 and 20 hours.
Comparing these two images shows that increasing
milling time will make particle size reduction which
means that the particle size will be smaller. This also
agreed with the XRD data analysis.
Magnetic properties of the obtained sintered
Fe2TiO5 samples were measured by VSM at room
temperature. Figure 7 shows hysteresis curves of 25
hours milled sample with various sintering
temperatures at 1100, 1200, and 1300oC for 1 hour. It
can be seen that powders before sintering process have
large magnetization because of the existence of Fe2O3
phase in the samples. Fe2O3 phase, even in TiO2 phase,
has ferromagnetic behavior, thus it will show magnetic
hysteresis curve.
The values of magnetic properties according to
their magnetization curves were summarized in Table
1. After sintering process, it was realized that there
was magnetic properties changing. The magnetic
parameter values become smaller. This is related to
formation of Fe2TiO5 phase and decreasing Fe2O3
phase in the samples. TiO2 phases also have influence
in the magnetic properties. The obtained samples
behave more paramagnetic as increasing sintering
temperature.
0.4
(a)
(b)
(c)
(d)
M (emu/g)
CONCLUSION
Nanoparticles of Fe2TiO5 have been successfully
synthesized by simple mechanical alloying method
using ball milling technique. The formation of Fe2TiO5
nanoparticles were followed by TiO2 as secondary
phase. The obtained Fe2TiO5 nanoparticles have
crystal size  51 nm measured by XRD peak profile
analysis and confirmed by SEM images observation.
The magnetic properties of the resulted samples have
small magnetization and more paramagnetic behavior
realized as increasing sintering temperature due to
decreasing Fe2O3 phase in the samples.
ACKNOWLEDGMENTS
Our team research would like to say thank you very
much to all collaborators who help the experimental
and analysis works. This work was supported by
“Hibah Penelitian Laboratorium dana BOPTN ITS”
with Number: 013674.135/IT2.7/PN.08.01/2013, date:
Mei 13, 2013.
REFERENCES
1. M. Tadic, N. Citakovic, M.Panjan, Journal of Alloys and
Compounds 509(28), 7639-7644 (2011).
2. Dorota Flak, Artur Braun, Antje Vollmer, Mieczyslaw
Rekas, Sensors and Actuators B 187, 347– 355, (2013).
3. A.L.Castro, M.R.Nunes, M.D.Carvalho, L.P.Ferreira, J.-
C.Jumas, F.M.Costa, M.H. Florêncio, Journal of Solid

0.0 State Chemistry 182(7), 1838–1845 (2009).

4. Kyung-Mi Min, Kyung-Soo Park, Ah-Hyeon Lim, Jae-
Chan Kim, Dong-Wan Kim, Ceramics International
38(7), 6009–6013 (2012).
5. R. Yu, Z. Li, D. Wang, X. Lai, C. Xing, M. Yang and X.
-0.4 Xing, Scripta Materialia 63(2), 155–158 (2010).
-1 0 1
6. Bodo Danzfuss And Ulrich Stimming, Electroanal
H (T) Chem. 164(1), 89-119 (1984).
FIGURE 7. Magnetic hysteresis curve of the sintered 7. J.K. Srivastava, J. Hammann, K. Asai, and K.
samples for 25 hours with various sintering temperatures: (a) Katsumata, Physics Letters A 149(9), 485-487 (1990).
before sintering; (b) 1100oC; (c) 1200oC; and (d) 1300oC. 8. M.R. Mohammadi, D.J.Fray, Physica E 46, 43–51
(2012).
9. H. Kozuka, and M. Kajimura, Journal of Sol-Gel Science
TABLE 1. Magnetic parameters of the sintered samples for
and Technology 22, 125-132 (2001).
25 hours with various sintering temperatures.
10. M. Sahebary, S. Raygan, S.A. Ebrahimi, Iranian Journal
Magnetic Properties
of Science and Technology 33(B5), 415-424, (2009).
Samples Hc Ms Mr 11. Jae Han Jho, Dong Hyun Kim, Sun-Jae Kim, Kyung Sub
(T) (emu/g) (emu/g) Lee, Journal of Alloys and Compounds 459(1-2), 386-
Milling for 25 hours 389 (2008).
0.069 0.385 0.149
Before sintering 12. A.M. Al-Saie, A. Al-Shater, S. Arekat, A. Jaffar, M.
Milling for 25 hours Bououdina. Ceramics International 39(4), 3803-3808
0.058 0.228 0.0084
at 1100oC (2013).
Milling for 25 hours
0.043 0.176 0.0082
at 1200oC
Milling for 25 hours
0031 0.129 0.015
at 1300oC

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