Advanced Powder Technology 24 (2013) 507–511

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Advanced Powder Technology

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

Original Paper

Thermal stability of silica-coated magnetite nanoparticles prepared by an

electrochemical method
Fauziatul Fajaroh a,b, Heru Setyawan b,⇑, Adrian Nur b, I. Wuled Lenggoro c
a
Department of Chemistry, Faculty of Mathematics and Natural Science, Malang State University, Jl. Semarang 5, Malang 65119, Indonesia
b
Department of Chemical Engineering, Faculty of Industrial Technology, Sepuluh Nopember Institute of Technology, Kampus ITS Sukolilo, Surabaya 60111, Indonesia
c
Department of Chemical Engineering, Graduate School of Bio-Applications and Systems Engineering, Tokyo University of Agriculture and Technology, Nakacho 2-24-16,
Koganei, Tokyo 184-8588, Japan

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

Article history: Magnetite nanoparticles have been prepared by electrooxidation of iron in water. Surface modifications
Received 22 May 2012 have been conducted by coating the nanoparticles with silica by a one-step synthesis in dilute sodium
Received in revised form 15 August 2012 silicate solution. The mean size of particles was approximately 10–30 nm for the uncoated particles
Accepted 15 September 2012
and 9–12 nm for the coated particles. The results obtained from thermal gravimetric/differential thermal
Available online 3 December 2012
analysis (TG/DTA) revealed that the silica layer formed by the electrochemical method was stable and
could serve as a protective layer. Annealing the nanoparticles at 550 °C for 30 min converts magnetite
Keywords:
into maghemite for the silica-coated particles, and it further converts the uncoated particles into hema-
Magnetite nanoparticles
Silica-coated
tite. The conversions cause the saturation magnetization to decrease for all samples.
Electrochemical method Ó 2012 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Thermal stability Technology Japan. All rights reserved.

1. Introduction silica-coated magnetite nanoparticles having superparamagnetic

Nanosized materials are of scientific and technological interest
because of their excellent properties that differ from their
corresponding bulk materials. Nanosized particles of iron oxides,
especially magnetite (Fe3O4) and maghemite (c-Fe2O3), have
numerous potential applications in magnetic recording technology,
pigments, catalysis, photocatalysis, medical uses and environmen-
tal processes. In biomedical applications, the nanoparticles have
been applied in targeted drug delivery [1] and hyperthermia
treatment [2]. In environmental processes, they are used for the
treatment of water and wastewater [3].
We previously reported on the preparation of magnetite nano-
particles by a surfactant-free electrochemical method using iron
as the sacrificial anode for the Fe source and water as the electrolyte
[4]. The main advantage of this method is that the particle size can
be controlled easily by adjusting the imposed electrooxidation cur-
rent density or potential to the system. The produced nanoparticles
were nearly monodispersed with a mean size ranging from 10 to
30 nm. They exhibited ferromagnetic properties with a relatively
high saturation magnetization, although some impurities in the
form of FeOOH, a nonmagnetic material, were retained. These
impurities could be eliminated by adding a small amount of
sodium silicate solution (100–200 ppm) to obtain high-purity
⇑ Corresponding author. Tel.: +62 31 5946240; fax: +62 31 5999282.
E-mail address: sheru@chem-eng.its.ac.id (H. Setyawan).
properties [5]. The sodium silicate could also act as a silica precur-
sor for the silica coating of magnetite nanoparticles once they were
formed to produce silica-coated magnetite nanoparticles. Hence,
we can prepare silica-coated magnetite nanoparticles by one step
in which the formation of magnetite particles and their coating is
conducted simultaneously. The silica-coated magnetite nanoparti-
cles exhibited an excellent stability in an acidic environment com-
pared with the uncoated ones.
It is well known that magnetite nanoparticles are very much
susceptible to air oxidation [6]. Heating magnetite nanoparticles
in an air environment may transform the nanoparticles to maghe-
mite (c-Fe2O3) and most likely continue to oxidize them further to
hematite (a-Fe2O3). Maghemite has the same crystalline structure
as magnetite, namely, spinel ferrite. Bulk maghemite possesses fer-
rimagnetic properties at room temperature, while hematite is anti-
ferromagnetic. Under laser irradiation, the thermal effect of light
can also induce the transformation of magnetite (Fe3O4) to maghe-
mite (c-Fe2O3) and finally to hematite (a-Fe2O3) [7]. To protect
magnetite nanoparticles from possible air oxidation, they are typ-
ically coated with a more inert material, such as silica [8]. The silica
coating on magnetic nanoparticles has several advantages: (i) it
screens the magnetic dipolar attraction between magnetic nano-
particles that favors the dispersion of magnetic nanoparticles in li-
quid media and protects them from dissolution in an acidic
environment, (ii) it can be functionalized with various functional
groups due to the existence of abundant silanol groups, and (iii)

0921-8831/$ - see front matter Ó 2012 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
http://dx.doi.org/10.1016/j.apt.2012.09.008
508 F. Fajaroh et al. / Advanced Powder Technology 24 (2013) 507–511

it provides an inert layer for magnetic nanoparticles in biological
systems. Therefore, in addition to chemical stability, it is important
to investigate thermal stability of magnetite and silica-coated mag-
netite nanoparticles under heating conditions. In addition, it is
common to increase the crystallinity of magnetite during synthesis
by annealing [9]. This makes the information about the transition
temperature important.
The present study reports on an investigation of the thermal
stability of silica-coated magnetite nanoparticles prepared by the
electrooxidation of iron in sodium silicate solution. The thermal ef-
fect of the treatment on the crystallinity and the magnetic proper-
ties of the particles are investigated.
2. Synthesis and characterization
The experiments were conducted in an electrochemical cell
made of acrylic resin with two electrodes. Details of the experi-
ment have been described elsewhere [4,5]. Briefly, pure iron to
be electrooxidized was prepared by electroplating an iron plate
of size (45  12) mm in FeSO4 solution. The electrooxidation was
carried out either in demineralized water or in dilute sodium sili-
cate solution (150 ppm and 200 ppm) to prepare silica-coated
magnetite nanoparticles. Previously, we have shown that the
silica-coated magnetite nanoparticles prepared using the sodium
silicate concentrations of 150 and 200 ppm had high crytallinity
[5]. On the other hand, the crystallinity was very low for the
silica-coated magnetite nanoparticles prepared using the sodium
silicate concentration of 300 ppm. The nanoparticles were not
formed by increasing further the sodium silicate concentration
due to the rapid coating of silica on the anode surface once the
electrooxidation started. Hence, only thermal stability of silica-
coated magnetite nanoparticles prepared using sodium silicate
concentrations of 150 and 200 ppm are investigated. The electro-
plated iron plate was connected with the positive terminal of a
DC power supply (the anode), and an unplated iron plate counter
electrode of the same size was connected to the negative terminal
(the cathode). The electrodes were set parallel with an interelectrode
spacing of 2 cm. The electrooxidation was conducted for 12 h at an
applied potential of 20 V. The particles produced were filtered, washed
with demineralized water and dried for characterization. The particles
synthesized in water and in 150 ppm and 200 ppm sodium silicate
solution will be referred to, respectively, as S1, S2 and S3.
The thermal stability of the as-synthesized magnetite nanopar-
ticles was studied by thermal gravimetric and differential thermal
analysis (TG–DTA) (Model TG8120, Rigaku Instrument). The sam-
ples were heated from room temperature to 600 °C at a heating
rate of 10 °C/min in static air. The structural phase identification
of the nanoparticles and the crystalline size calculations were car-
ried out using a Rigaku Instrument RINT2100VPC/N X-ray diffrac-
tometer with Cu Ka radiation at room temperature in the 2h
interval of 10–90° at a scan rate of 1.25°/min. The X-ray diffraction
(XRD) patterns were taken after annealing the samples in a furnace
at a temperature of 550 °C for 30 min. Magnetic characterization
was performed using a vibrating sample magnetometer (Type
1.2H VSM, Oxford). Infrared (IR) spectra were recorded using an
FTIR spectrophotometer (FTIR 8400s, Shimadzu). The morphology
of particles was observed by scanning electron microscopy (SEM;
FE-SEM JSM-6335F, JEOL).
3. Results and discussion
3.1. Thermal analysis
Fig. 1 shows the SEM images of the samples synthesized by
electrooxidation of iron in demineralized water (S1) and in
150 ppm sodium silicate solution (S2). The mean size of particles
is approximately 20 nm for S1 and 12 nm for S2 that corresponds
to a BET surface area of approximately 52 and 117 m2/g, respec-
tively. The particles are nearly spherical in shape for both cases.
The effect of the operating conditions on particle size has been
investigated in our previous work, and S3, the mean particle size
is approximately 9 nm that corresponds to a BET surface area of
approximately 135 m2/g [4,5]. Below, we discuss the thermal sta-
bility of the particles, both uncoated and silica-coated magnetite
nanoparticles, when they are heated up to 600 °C.
Fig. 2 shows the thermal gravimetric analysis of the samples of
magnetite nanoparticles S1, S2 and S3. It can be detected that the
three samples exhibit a weight reduction of 8.83%, 11.01% and
14.84% for S1, S2 and S3, respectively. For all three samples, there
are two weight reduction steps: from room temperature to 100 °C
and at >100 °C. The general shapes for magnetite (S1) and silica-
coated magnetite nanoparticles are very similar. This indicates that
the silica film is thermally stable and that the weight reduction in
silica-coated magnetite nanoparticles essentially occurs because of
species other than silica, e.g., physically adsorbed water or iron
oxide.
The first weight loss is detected from room temperature to
100 °C. The weight of all samples initially decreases and then
gradually increases. This indicates the loss of physically adsorbed
water on the particles. The losses of the physically adsorbed
water are 3.8%, 4.1% and 5.0% for S1, S2 and S3, respectively.
The amount of the physically adsorbed water is likely to be re-
lated to the particle surface area; small particles have high spe-
cific surface area. In the present study, S1 has the largest size,
and S3 has the smallest size, which results in S1 having the small-
est weight loss and S3 having the highest weight loss in the tem-
perature range.
In the temperature range from 100 °C to approximately
140 °C, the weight of silica-coated magnetite particles (S2 and
S3) is relatively constant, as shown more clearly by the time
changes of sample weight dW/dt, and then increases slowly until
a temperature of approximately 184 °C. In contrast, the weight of
uncoated particles (S1) increases continuously from 100 °C to
184 °C. This weight gain may come from the oxidation of Fe2+
in the magnetite particles. Magnetite in a dry state is readily oxi-
dized to maghemite (c-Fe3O3) by air and it reaches the maximum
amount at a temperature of approximately 270 °C [6,10]. The
transformation proceeds further to hematite (a-Fe3O3) and
reaches a maximum amount at a temperature of approximately
320 °C [10]. In the transformation, a mixed phase of Fe(II)(1 x)-
Fe(III)(2+x)O(4+0.5x), with less Fe(II), more Fe(III) and more cation
vacancies, is initially formed. When the reaction proceeds, the
density of the starting material decreases, and the weight in-
creases because oxygen is taken up according to the following
reaction: 4Fe3O4 + O2 ? 6Fe2O3.
The differential thermal analysis of the samples displayed in
Fig. 3 shows that there is an endothermic peak at a temperature
below 100 °C that corresponds to desorption of water. In addition,
there is also a high peak at a temperature of approximately 335 °C
for sample S1, indicating an exothermic reaction of the magnetite
conversion into maghemite and probably continue partially to
hematite. The peak also appears for samples S2 and S3, but it is
much lower, and for sample S3 the peak is very small. As it will
be shown later, XRD pattern of samples S2 and S3 after annealing
at 550 °C exhibits that for the cases of S2 and S3 magnetite is con-
verted into maghemite, and there is no further transition to hema-
tite. On the other hand, the XRD pattern of sample S1 indicates the
conversion of magnetite into maghemite and then partially into
hematite. This indicates that the silica-coated film is thermally sta-
ble and can protect magnetite from reaction with oxygen, which
supports the interpretation of the weight loss.
 F. Fajaroh et al. / Advanced Powder Technology 24 (2013) 507–511 509

Fig. 1. SEM images for samples S1 (uncoated) and S2 (silica-coated).

0 JCPDS 33-0664 (α -Fe2O3)

-2 0.0 JCPDS 39-1346 (γ-Fe2O3)

JCPDS 19-0629 (Fe3O4)

-4

dW/dt (wt% min )

-1
-0.2
Weight loss (%)

S1
-6 o
S3 550 C

Intensity (a.u.)
S2
-8 -0.4 S3 RT
S3
-10 S2 550 C
o

-0.6
-12 S2 RT
-14 -0.8 o
S1 550 C
-16
100 200 300 400 500 600 S1 RT
o
Temperature ( C) 25 30 35 40 45 50 55 60 65
2 θ (degree)
Fig. 2. Thermal gravimetric analysis of uncoated sample S1 and silica-coated
samples S2 and S3.
Fig. 4. XRD patterns of samples S1, S2 and S3 before and after annealing at 550 °C
for 30 min.

10

57.1° (5 1 1) and 62.6° (4 4 0), which match the standard pattern

0 of Fe3O4 (JCPDS 19-0629) well. After annealing, there are six char-
acteristic peaks for all samples at 30.3° (2 2 0), 35.7° (3 1 1), 43.3°
-10 (4 0 0), 53.7° (4 2 2), 57.4° (5 1 1) and 63° (4 4 0) that correspond to
Heat flow ( V)

c-Fe2O3 (JCPDS 39-1346). It can be observed that heating the par-

S3 ticles up to 550 °C for 30 min converts magnetite into maghemite
-20
S2 for samples S2 and S3. The conversion proceeds partially to hema-
S1 tite for sample S1 as indicated by, in addition to the characteristic
-30 peaks of c-Fe2O3, there are also eigth characteristic peaks at 33.2°
(1 0 4), 35.6° (1 1 0), 40.6° (1 1 3), 49.7° (0 2 4), 54.2° (1 1 6), 57.5°
-40 (0 1 8), 62.5° (2 1 4) and 64° (3 0 0) that match the standard pattern
of a-Fe2O3 (JCPDS 33-0664).
Fig. 5 shows the FTIR spectra of sample S2 before and after
-50
100 200 300 400 500 600 annealing. It can be observed that the bands that correspond to
o SiO2, i.e., at approximately 1080, 996, and 624 cm 1, still appear
Temperature ( C)
after annealing [11]. This indicates that silica film on the magnetite
Fig. 3. Differential thermal analysis of uncoated sample S1 and silica-coated surface is thermally stable. The inset in Fig. 5 shows the spectra at
samples S2 and S3. an enlarged scale to show the wavenumber range in more detail.
For the unannealed sample, there are two bands at approximately
580 and 442 cm 1 that correspond to magnetite [4]. After anneal-
3.2. Thermal effects on particle characteristics ing at 550 °C, more bands appear at approximately 700 cm 1, from
640 to 660 cm 1, and at approximately 580, 560, 460 and 430 cm 1
To understand the effects of heating on the characteristics of that can be attributed to maghemite [6,12]. These XRD and FTIR re-
magnetite, the particles were annealed at a temperature of sults corroborate the results of thermal analysis regarding the
550 °C for 30 min. Fig. 4 shows the XRD patterns of all three sam- transformation of magnetite to maghemite and, for sample S1,
ples after they were annealed at 550 °C. For comparison, the XRD the further transformation to hematite. The results also indicate
patterns of particles without annealing, referred to as being at that the silica film is thermally stable and can protect magnetite
room temperature (RT), are also presented. The patterns for all from oxidation.
samples before annealing have seven characteristic peaks at The crystallinity of magnetite slightly increases after annealing,
30.2° (2 2 0), 35.5° (3 1 1), 37° (2 2 2), 43.1° (4 0 0), 53.4° (4 2 2), as indicated by the sharper peaks of the XRD patterns shown in
510 F. Fajaroh et al. / Advanced Powder Technology 24 (2013) 507–511

Fig. 5. FTIR spectra of sample S2 before and after annealing at 550 °C for 30 min
(inset: enlarged scale).

Table 1
Crystallite size of samples S1, S2 and S3 before and after annealing at 550 °C,
calculated by the Scherrer formula.

Sample Crystallite size (nm)

Before annealing After annealing
S1 22 23
S2 16 22
S3 16 20

Fig. 4. Table 1 shows the crystallite size of magnetite, as calculated

by the Scherrer formula. It can be observed that the crystallite size
for the three samples is not influenced significantly by annealing
them at 550 °C for 30 min. This indicates that silica film can serve
as a protective coating.
The magnetic properties of particles before and after annealing
were examined with VSM at room temperature. Fig. 6 shows the
magnetization curve for samples S1 (a), S2 (b) and S3 (c) before
and after annealing. The results indicate that for all samples, the
nanoparticles likely possess ferromagnetic properties, as indicated
by a hysteresis loop, which is typically observed for ferromagnetic
materials of sizes larger than 10 nm. The saturation magnetization
of the nanoparticles decreases after annealing for all samples. As
discussed before, after annealing at 550 °C, magnetite is converted
into maghemite. The saturation magnetization of bulk maghemite
material is approximately 80 emu/g, and that of magnetite is
approximately 90 emu/g [13]. Thus, it could be expected that
maghemite nanoparticles with the same size of magnetite would
have lower saturation magnetization.

4. Conclusions

It has been demonstrated by the results of TG/DTA that the sil-

ica layer formed on the magnetite nanoparticles prepared by the
electrooxidation of iron in sodium silicate solution is stable under
Fig. 6. Magnetization curves of samples before and after annealing at 550 °C for
heating up to 550 °C. The silica layer appears to be effective in pro-
30 min for samples (a) S1, (b) S2, and (c) S3.
tecting magnetite from being converted to other oxide species.
Heating the nanoparticles at 550 °C for 30 min converts magnetite
into maghemite for the silica-coated particles, and the uncoated
particles are further converted into hematite. The heating also that may be caused by the conversions of magnetite to other oxide
causes the decrease in the saturation magnetization of magnetite species, such as maghemite or hematite.
 F. Fajaroh et al. / Advanced Powder Technology 24 (2013) 507–511
Acknowledgements
We would like to thank the Directorate General of Higher Edu-
cation (DGHE), the Ministry of Education and Culture, Indonesia,
for funding and for the financial support for one of the authors
(F.F.) to obtain a doctorate through BPPS and to visit the Tokyo Uni-
versity of Agriculture and Technology as a research fellow via a
Sandwich-Like Program. We also thank Ms. Doris Nekesha for her
assistance with the experiments.
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