J Therm Anal Calorim (2016) 125:1185–1198
DOI 10.1007/s10973-016-5393-y
Investigation of magnetite nanoparticles stability in air by thermal
analysis and FTIR spectroscopy
Marcela Stoia1,2 • Roxana Istratie1 • Cornelia Păcurariu1
Received: 2 November 2015 / Accepted: 7 March 2016 / Published online: 24 March 2016
Ó Akadémiai Kiadó, Budapest, Hungary 2016
Abstract Magnetic iron oxides were prepared by pre-
cipitation of Fe(II) hydroxide using different precipitation
agents: ammonia, benzylamine and sodium hydroxide,
followed by oxidation with the oxygen dissolved in water.
Thermal analysis, coupled with FTIR spectroscopy, has
evidenced the formation of a mixture of magnetite and
maghemite, with a higher content of magnetite in case of
the powder synthesized with benzylamine. The stability of
magnetite at oxidation by air during storage at room tem-
perature and 60 °C was investigated by means of TG/DSC
simultaneous thermal analysis, FTIR spectroscopy and
X-ray diffractometry. Thermal analysis evidenced an
exothermic process with mass gain in temperature range
100–190 °C, corresponding to magnetite oxidation process,
but due to the superposition of other processes it could not
offer quantitative information. FTIR spectroscopy has
provided, especially through the first and second deriva-
tives of FTIR spectra, the most valuable information
regarding the evolution of magnetite to maghemite, due to
their different characteristic bands. XRD technique has
evidenced a slight shift of the main diffraction peaks at
higher 2-theta values during the evolution of magnetite to
maghemite. According to thermal analysis data, the powder
synthesized with ammonia was completely oxidized after
15 days, while the other two powders, synthesized with
& Marcela Stoia
marcela.stoia@chim.upt.ro; marcela.stoia@upt.ro
1
Faculty of Industrial Chemistry and Environmental
Engineering, Politehnica University Timişoara, 6 Pı̂rvan Blv.,
300223 Timisoara, Romania
2 [16]. The heating of magnetite nanoparticles in air at low
Research Institute for Renewable Energy, Politehnica
University Timişoara, P-ta Victoriei No.2, 300006 Timisoara,
Romania
benzylamine and sodium hydroxide, were completely
oxidized after 110 days of keeping in air at room temper-
ature. For a temperature of 60 °C, the oxidation was much
faster; the oxidation process of the powder synthesized
with benzylamine disappeared from TG/DSC curves after
1 day. All final powders were formed from nanoparticles
with diameters up to 25 nm, with magnetic properties
characteristic to nanometric maghemite.
Keywords Magnetite  Stability  Oxidation 
Thermal analysis  FTIR spectroscopy
Introduction
Magnetic nanoparticles of iron oxides such as Fe3O4 and c-
Fe2O3 have attracted attention in biomedical applications
such as drug delivery systems, magnetic resonance imaging
(MRI) and cancer therapy [1–3] because of their biocom-
patibility and low toxicity in the human body [4]. Recently,
magnetic materials have gained special attention as
adsorbents in water purification due to their numerous
advantages such as high separation efficiency, simple
manipulation process and soft operation conditions [5, 6].
Many synthesis routes were developed for obtaining
magnetite such as coprecipitation of Fe(II) and Fe(III)
hydroxides [7], precipitation of Fe(II) hydroxide and oxi-
dation [8], spray pyrolysis [9], sol–gel [10], thermal
decomposition of different precursors [11], combustion
[12], hydrothermal [13], solvothermal [6, 14] and ball
milling [15]. However, magnetite nanoparticles are very
much susceptible to air oxidation even at low temperatures
temperatures leads to maghemite, while at higher temper-
atures maghemite is further oxidized to hematite [17].
123
1186 M. Stoia et al.

3500
Magnetite, Fe3O4
transformation of ultrafine magnetite particles to c-Fe2O3
Magnetite, γ – Fe2O3
Goethite, FeO(OH) made in order to clarify quantitatively the catalytic activity
3000
of fine magnetite powders was reported by Haneda and
2500 Morrish [22]. A comparison of behavior to oxidation of
Intensity/counts

(A) magnetite micro- and nanopowders was made by means of

2000
1500
1000
500
0
10 20 30 40
2θ /°
Fig. 1 XRD patterns of the initial powders (dried at room temper-
ature in vacuum oven)
Maghemite has the same crystalline structure as magnetite,
namely spinel ferrite. Bulk magnetite and maghemite
possess ferrimagnetic properties at room temperature [18].
It has been shown that the thermal stability of magnetite
depends mostly on the grain size, the rate of oxidation [19]
and the fabrication procedure [20]. Thus, at bulk level the
oxidation of magnetite to hematite at room temperature is
inhibited, and changes in the crystalline structure can be
achieved only by heating up to 600 °C; at the nanoscale
level, changes in the crystalline structure can be expected
and observed at much lower temperatures, even very close
to the room temperature [19, 20].
The conversion of magnetite to maghemite has been
studied by several investigators [17, 18, 21]; they have
established that the Fe3O4 oxidation to c-Fe2O3 can be
accomplished at approximately 220 °C. However, almost
all these studies have been made on micron- or close-to-
micron-sized particles, commonly used as active ingredi-
ents of magnetic recording tapes. A kinetic study of the
thermogravimetric analysis and IR and Raman spec-
troscopy by Li et al. [23].
(B) Due to this susceptibility to oxidation, it is very difficult
to synthesize and stabilize pure magnetite; in most of the
(H) cases, a mixture of magnetite and maghemite is obtained,
and the quantification of each phase in such mixtures is
50 60 70 80 quite difficult [24]. Crystalline phase composition of iron
oxides mixtures was investigated by various techniques
such as X-ray diffraction (XRD) [24, 25], Mössbauer
spectroscopy (MS) [26, 27], FTIR spectroscopy [28],
Raman spectroscopy [23] and X-ray photoelectron
spectroscopy (XPS) [29]. Some of these techniques are
expensive and are not available for all research
laboratories.
This work reports the synthesis of magnetite at room
temperature by precipitation method starting from FeSO4-
7H2O and using comparatively benzylamine, NH3 and
NaOH as precipitants. A systematic study of the stability of
the obtained magnetite in air, in time, at 25 and 60 °C, was
investigated by TG/DSC, FTIR and XRD techniques,
which are usual techniques, present in any research
laboratory.
Experimental
Materials
The starting materials were as follows: ferrous sulfate
heptahydrate (FeSO47H2O) (Sigma-Aldrich C99 %),
benzylamine (C6H5CH2NH2) (Sigma-Aldrich, C99 %),

Table 1 Position of the main diffraction peaks of the synthesized sample and of the references
No. A0 B0 H0 Magnetite PDF file 01-080-6407 Maghemite PDF file 00-039-1346 (h, k, l)

1 18.24 18.21 18.1915 18.28 18.38 (1, 1, 1)

2 29.99 29.96 30.52 30.07 30.24 (2, 2, 0)
3 35.34 35.27 35.28 35.41 35.63 (3, 1, 1)
4 37.04 37.00 36.49 37.05 37.25 (2, 2, 2)
5 43.04 42.99 42.99 43.05 43.28 (4, 0, 0)
6 53.45 53.34 53.29 53.40 53.73 (4, 2, 2)
7 57.02 56.91 56.81 56.92 57.27 (5, 1, 1)
8 62.59 62.45 62.40 62.51 62.92 (4, 4, 0)
9 71.10 71.06 70.86 70.91 71.37 (6, 2, 0)
10 74.14 73.98 73.95 73.94 74.47 (5, 3, 3)
11 75.08 75.02 75.23 74.94 75.44 (6, 2, 2)
12 79.21 79.16 78.90 78.90 79.44 (4, 4, 4)

123
Investigation of magnetite nanoparticles stability in air by thermal analysis and FTIR spectroscopy 1187

Fig. 2 TG/DTG/DSC curves of

DSC/mW mg–1
120

DTG/% min–1
170 0,8
initial powders: a A; b B; c H 0
100 Exo
0,6

–1 0,4

99 0,2

Mass/%
563 –2
DTG
0,0

DSC –0,2
98 –3

–0,4

TG
(a) –4 –0,6
97
100 200 300 400 500 600 700
Temperature/C

1,0
128

DSC/mW mg–1

DTG/% min–1
0
100 Exo 0,5

–1 0,0
576
Mass/%

99
DSC –0,5
–2

DTG
–1,0
98
–3
–1,5
TG

(b)
97 –4 –2,0
100 200 300 400 500 600 700
Temperature/C
1,0
142
DSC/mW mg–1

DTG/% min–1
0
100 Exo
0,5

–1
DTG
0,0
Mass/%

99

DSC
–2
–0,5

98
–3
–1,0
TG

(c)
97 –4 –1,5
100 200 300 400 500 600 700
Temperature/C

123
1188
(A)
1631
(B) 3415
Transmittance/a.u.
1635
3415
(H)
1629
3410
3126
4000 3500 3000 2500 2000 1500
Wavenumber/cm–1
Fig. 3 FTIR spectra of the initial, as-synthesized powders
ammonium hydroxide solution puriss. p.a., 25 % NH3 in H2O
(Sigma-Aldrich), sulfuric acid (H2SO4) 98 % (Merck Milli-
pore) and sodium hydroxide (NaOH) p.a (98 %, Lach:ner).
All reagents were used without further purification.
Synthesis
The synthesis took place in a 400 cm3 beaker. The quantity
of FeSO47H2O necessary for the synthesis of 0.01 mol of
Fe3O4 was dissolved in 100 cm3 distilled water, under
addition in drops of H2SO4 6 M, until complete dissolu-
tion. The obtained clear solution was neutralized by addi-
tion of the corresponding precipitant, until the precipitation
of iron hydroxide starts. At that moment, the calculated
volume of amine (corresponding to an excess of 50 % to
the stoichiometric quantity necessary for the precipitation
of ferrous hydroxide) was quickly added to the ferrous
sulfate solution. A greenish-black precipitate was obtained,
which was kept under magnetic stirring for 60 min. In case
of benzylamine, after precipitation, the final pH value was
8.5, and 2 mL of NH3 solution was added to increase the
final pH up to 9. The final color of the precipitate became
dark-gray and presented magnetic properties (under the
action of a usual magnet). The obtained suspension was left
for 24 h (in the dark) for partial oxidation of Fe2? to Fe3?
with water dissolved oxygen (which can be considered as a
modified Ueda synthesis methods [30, 31]). Finally, the
precipitate was separated by filtration, washed with a hydro-
ethanolic solution (volume ratio H2O/C2H5OH = 1: 1) and
123
M. Stoia et al.
then with absolute ethanol and dried in a vacuum oven at
room temperature, to avoid the oxidation. Three synthesis
were performed using NH3 (sample A), benzylamine
(sample B) and NaOH (sample H) as precipitants.
The obtained powders have been kept in air, in a des-
418
iccator, at 25 °C, and were studied regarding their stability
to oxidation in air and in time, using TG/DTG/DSC cou-
574
pled thermal analysis, FTIR spectroscopy and X-ray
diffractometry. A part of sample B was also kept in an oven
at 60 °C and similarly investigated.
Characterization techniques
574
Thermal behavior of the powders was studied using a
794
Netzsch STA 449C instrument, in air atmosphere at a flow
rate of 20 mL min-1. The TG/DSC curves were recorded
893
in the range of 25–1000 °C with a heating rate of
578
10 K min-1, using alumina crucibles. The phase compo-
sition of the samples was determined by XRD, using a
1000 500 Rigaku Ultima IV diffractometer (CuKa radiation). FTIR
spectra were carried out using a Shimadzu Prestige-21
spectrometer in the range 400–4000 cm-1, using KBr
pellets and resolution of 4 cm-1. Preliminary spectrum
treatment involved 23-point smoothing with fast Fourier
transform filtering and baseline correction by subtracting a
linear baseline fitted between the first and last points. All
first- and second-derivative FTIR spectra were obtained
after 23-point smoothing of the as-processed spectra. The
morphology of the nanopowders was investigated by
scanning electron microscopy (SEM), using a FEI Quanta
FEG 250 microscope. The magnetic investigation of the
final nanopowders was carried out at room temperature
under AC (50 Hz) applied magnetic fields of amplitudes up
to 4 kOe by means of an integrating fluxmeter-type hys-
teresis graph described elsewhere [32].
Results and discussion
The powders obtained by drying the obtained precipitates
in a vacuum oven for 24 h were first characterized by
X-ray diffractometry. The XRD patterns of the three
powders (A, B, H) are shown in Fig. 1. According to the
database PDF 4? [33], the samples A and B contain a
spinelic phase as the only crystalline phase; due to the
similarity of the XRD patterns of magnetite and maghe-
mite, it is difficult to establish which phase is present, or
the composition of their mixture. In case of sample H
(obtained with NaOH), a second phase is present beside
magnetite, identified as goethite (FeO(OH)). The compo-
sition of the mixture, estimated from XRD data, was 42 %
goethite and 58 % spinelic phase, which can be magnetite
or a mixture of magnetite–maghemite. In order to make a
Investigation of magnetite nanoparticles stability in air by thermal analysis and FTIR spectroscopy 1189

101.5 102.0
101.0 101.5
101.0
100.5 100.5
100.0
100.0 99.5 initial
99.5 99.0
1 day

Mass/%
98.5
Mass/%

99.0 98.0 2 days

97.5
98.5 97.0 3 days
initial
96.5 15 days
98.0
1 day 96.0 29 days
97.5 95.5
2 days 60 days
95.0
97.0 3 days 90 days
94.5
96.5 15 days 94.0 110 days
93.5
96.0 (a) 93.0 (b)
92.5
100 200 300 400 500 600 700 100 200 300 400 500 600 700
Temperature/°C Temperature/°C
104 101.5
103 101.0
102
101 100.5
100 100.0
99
99.5
98 initial
Mass/%

Mass/%
97 1 day 99.0
96 2 days 98.5
95 3 days
94 98.0 initial
15 days
93 29 days 97.5
92 60 days 1 day
97.0
91
90 days
90 96.5 2 days
89 (c) 110 days (d)
96.0
88
100 200 300 400 500 600 700 100 200 300 400 500 600 700
Temperature/°C Temperature/°C

Fig. 4 TG curves at different time intervals in air at room temperature of samples a A, b B and c H and of sample B at 60 °C (d)

comparison between our samples and magnetite and
maghemite references, Table 1 shows the position (2 Theta
values) of the main visible peaks from the XRD patterns of
samples (we have excluded the peaks related to goethite
phase) and the corresponding lines of magnetite and
maghemite references. One can notice that our samples
have diffraction peaks close to those of magnetite, while all
maghemite lines are located at 2-theta values slightly
higher than those of magnetite phase. This difference of
2-theta values of diffraction peaks maxima, even if not so
significant, allows the quantification of each phase by
deconvolution of (5, 1, 1) diffraction peak [24] and can be
considered as an indicator for magnetite presence.
Olowe et al. [34] and Refait et al. [35] studied the
alkalization reaction of ferrous ions as regards the forma-
tion of iron hydroxide and iron oxide, and they proposed
the following reactions as the mechanism of formation of
Fe3O4:
Fe2þ þ 2OH ! Fe ðOHÞ2
3FeðOHÞ2 þ1=2O2 ! FeðOHÞ2 þ2FeOOH þ H2 O ð2Þ
FeðOHÞ2 þ2FeOOH ! Fe3 O4 þ 2H2 O ð3Þ
According to this mechanism, Fe3O4 is formed as a
result of the dehydration reaction of ferrous hydroxide and
ferric oxyhydroxide (Eq. 3), the latter compound being
produced by the partial oxidation of ferrous hydroxide by
the dissolved O2 (Eq. 2) [36]. The presence of ferric oxy-
hydroxide in the sample obtained with NaOH confirms this
mechanism. It has been shown that ‘hydrolyzed’ ferrous
iron species are more readily oxidized than non-hydrolyzed
ferrous species in the following order [Fe(OH)2] [
[Fe(OH)]? [ Fe2?, explained by the fact that OH- ligands
donate electron density to the metal ion which increases its
reducing power and stabilizes the Fe3? formed during the
oxidation [37].
The presence of magnetite in the synthesized powders
can be evidenced by thermal analysis based on the
exothermic process of Fe(II) oxidation to Fe(III), with mass
ð1Þ gain, which appears, according to the literature [29], up to
200 °C. Due to the low temperature used in the synthesis,

123
1190 M. Stoia et al.

Table 2 Mass gain (%) in the range 100–190 °C at different time
intervals
Sample Temperature/°C Time/days Mass change
(100–190 °C)/%
A 25 0 ?0.14
1 ?0.09
2 ?0.07
3 ?0.05
15 20.03
B 25 0 ?0.31
1 ?0.29
2 ?0.28
3 ?0.24
15 ?0.17
29 ?0.13
60 ?0.09
90 ?0.05
110 0.0
H 25 0 ?0.12
1 ?0.11
2 ?0.11
3 ?0.10
15 ?0.07
29 ?0.05
60 ?0.04
90 ?0.03
110 ?0.01
B 60 0 ?0.31
1 20.07
the obtained powders can have a significant amount of
–OH groups on its surface; thus, the endothermic process
of the surface –OH groups and H2O molecules elimination
can overlap with the oxidation process. This makes difficult
a potential quantification of magnetite content in the
product. However, the presence of this exothermic process
with mass gain can be used as a fingerprint for magnetite.
Taking into account the XRD results, we expected to
confirm the presence of magnetite through TG/DTG/DSC
coupled thermal analysis. The obtained curves are shown in
Fig. 2a–c.
The TG/DTG/DSC curves evidence in all initial samples
the presence of magnetite or a mixture of magnetite and
probably maghemite; in case of sample H, according to
XRD results (Fig. 1) magnetite and maghemite are also
mixed with goethite. The presence of magnetite was con-
firmed by the exothermic process with mass gain in the
temperature range 100–190 °C, corresponding to Fe3O4
oxidation to Fe2O3 (theoretically, for pure magnetite the
mass gain should be 3.45 %). This process is preceded by
an endothermic process with mass loss, due to the
elimination of hydrogen-bonded water molecules from
particles surface. This process overlaps with the oxidation
of magnetite. Sample A, obtained with NH3 as precipitant,
exhibits the lowest mass gain (?0.14 %) in the range
100–180 °C (the maximum of the exothermic effect at
120 °C). This may be caused by the superposition of
another weak exothermic process at *170 °C which
occurs with mass loss, and it is probably related to the
elimination of residual NH3 bonded on particles surface, as
it is visible only in this case. The mass loss that takes place
up to 400 °C may be due to the dehydroxylation, but there
are no significant thermal effects. Another exothermic
process, with no mass change, takes place around 560 °C
and corresponds to the transition of maghemite (c-Fe2O3)
to hematite (a-Fe2O3) [38, 39].
Sample B, obtained with benzylamine as precipitant,
exhibits a higher mass loss (0.31 %) and an exothermic
effect with maximum at 128 °C. This process continues
with a mass loss up to 400 °C, and then the mass remains
constant. The exothermic effect due to the maghemite–
hematite transition is located at 576 °C.
In case of sample H, obtained by precipitation of Fe2?
with NaOH, after the first mass loss up to 100 °C, a mass
gain of ?0.12 %, associated with the exothermic effect
with maximum at 142 °C, followed by mass loss up to
400 °C can be observed. In this case, the exothermic effect
associated with the transition of maghemite to hematite is
almost absent due to the lower maghemite content in the
sample [40].
FTIR spectroscopy was also used in order to evidence
the formation of maghemite–magnetite mixture in the ini-
tial samples. According to the literature [41, 42], FTIR
spectrum of magnetite exhibits two strong infrared
absorption bands at 570 and 390 cm-1. According to Ishii
and Nakahira [41], these bands can be assigned to the Fe–O
stretching mode of the tetrahedral and octahedral sites (the
band at 570 cm-1) and to the Fe–O stretching mode of the
octahedral sites (the band at 390 cm-1). Maghemite, a
defective form of magnetite, has absorption bands at 630,
590 and 430 cm-1 [42]. Goethite has –OH stretching
vibrations at *3125, *890 and *800 cm-1 assigned to
m-OH, d-OH and c-OH, respectively [43], and bands
characteristic to Fe–O stretching, located around 400 and
630 cm-1 (weak) [28]. The two bands at 893 cm-1 (–OH)
and 794 cm-1 (–OH) are important diagnostic bands of
goethite [40]. Due to these differences, the FTIR spectrum
can be considered one of the most appropriate tools for
confirming the purity of an iron oxide, or to evidence the
presence of a mixture of iron oxides. Figure 3 shows the
FTIR spectra of the initial powders: A, B and H.
By analyzing the FTIR spectra, we can conclude that the
powder A consists in a mixture of magnetite and maghe-
mite, based on the fact that the band located at 574 cm-1 is

123
Investigation of magnetite nanoparticles stability in air by thermal analysis and FTIR spectroscopy 1191

initial
initial
1 day initial
1 day
2 days
1 day

3 days 574 2 days

Transmittance/a.u.

2 days
15 days 3 days

T%/(cm–1)2
578
3 days

T%/cm–1
28 days
15 days
584 15 days
60 days
28 days
573
28 days
90 days
619 586 60 days
60 days
110 days 627
571 440
90 days
90 days
621
572
110 days
441 110 days
627 578

(a) 627 578 (b) (c)

1200 1050 900 750 600 450 1200 1050 900 750 600 450 1200 1050 900 750 600 450
Wavenumber/cm–1 Wavenumber/cm–1 Wavenumber/cm–1

Fig. 5 Evolution in time of FTIR spectra (a), their first (b) and second (c) derivatives for sample A in air at 25 °C

initial
initial

1 day initial
1 day

2 days
2 days
1 day
572
3 days
2 days 3 days
Transmittance/a.u.

578
15 days
T%/(cm–1)2

3 days 15 days
T%/cm–1

28 days 582
15 days
28 days

60 days 582
28 days 60 days
572
90 days
60 days
110 days 573 90 days

90 days
578
110 days
110 days

570
(a) 628 (b) (c)
584
1200 1050 900 750 600 450 1200 1050 900 750 600 450 1200 1050 900 750 600 450
Wavenumber/cm–1 Wavenumber/cm–1 Wavenumber/cm–1

Fig. 6 Evolution in time of FTIR spectra (a), their first (b) and second (c) derivatives for sample B in air at 25 °C

not symmetric; some weak bands of maghemite may be stretching vibration bands at 3410 and 1629 cm-1 and
also present. The powder B contains mostly magnetite as three –OH vibration bands at 3126, 893 and 794 cm-1. The
the band located at 574 cm-1 is sharp and symmetric and strong asymmetrical band at 578 cm-1 characteristic to
there is only a weak shoulder around 420 cm-1. In case of Fe–O stretching vibrations includes also the Fe–OH
powder H, the FTIR spectrum shows water molecule vibration band located at *630 cm-1 and possible Fe–O

123
1192 M. Stoia et al.

initial

initial
1 day initial

1 day
1 day
2 days 574
793
2 days
3 days
893 2 days
Transmittance/a.u.

578
794
3 days
894
3 days

T%/(cm–1)2
15 days 618 584

T%/cm–1
15 days
28 days
15 days
796 613 573
894
28 days
60 days 619 586 28 days

60 days
617 588 60 days
90 days
796
896
624 90 days
578
110 days 90 days
796
896
621 110 days
110 days
796
896
(a) 624 588 (b) (c)
1200 1050 900 750 600 450 1200 1050 900 750 600 450 1200 1050 900 750 600 450
Wavenumber/cm–1 Wavenumber/cm–1 Wavenumber/cm–1

Fig. 7 Evolution in time of FTIR spectra (a), their first (b) and second (c) derivatives for sample H in air at 25 °C

initial

initial
1 day initial
Transmittance/a.u.

2 days
410 1 day
T%/(cm–1)2
T%/cm–1

1 day

5 days 574
2 days 2 days
623 577
449

5 days
628 578
5 days

634 584
(a) (b) (c)
1200 1050 900 750 600 450 1200 1050 900 750 600 450 1200 1050 900 750 600 450
Wavenumber/cm–1 Wavenumber/cm–1 Wavenumber/cm–1

Fig. 8 Evolution in time of FTIR spectra (a), their first (b) and second (c) derivatives for sample B in air at 60 °C

vibration bands of maghemite (*635 cm-1). Thus, powder visible anymore starting with day 15, while in case of
H contains a goethite/magnetite/maghemite mixture, con- sample B, the mass gain is 0 only after 110 day. This
firming the conclusions of both XRD and thermal analysis difference in stability may be due to the adsorption of
study. benzylamine on particles surface, protecting Fe(II) ions
The stability in time of magnetite from the obtained from oxidation, and to the lower magnetite content in
powders was investigated during the storing in air, in a sample A. For sample H, due to the higher total mass loss
desiccator, at 25 °C. The TG curves of all three samples at (7 % compared with *3 % in case of sample B), the mass
various intervals, up to 110 days, are shown in Fig. 4a–c. gain is less evident. In order to better point the evolution of
From the TG curves recorded at different time periods, we the oxidation process, the mass gain registered is listed for
can see that, in case of sample A, the mass gain is not all three samples in Table 2. Due to the superposition of

123
Investigation of magnetite nanoparticles stability in air by thermal analysis and FTIR spectroscopy 1193

Fig. 9 XRD patterns of sample 14000

A during storing in air at 25 °C
110 days
12000

90 days
10000
60 days

Intensity/counts
8000 29 days

15 days
6000

3 days
4000
2 days

2000 1 day

initial
0
10 20 30 40 50 60 70 80 35 36

2θ /°

Fig. 10 XRD patterns of 14000

sample B during storing in
air at 25 °C 110 days
12000

90 days
10000
60 days
Intensity/counts

8000 29 days

15 days
6000

3 days

4000
2 days

2000 1 day

initial
0
10 20 30 40 50 60 70 80 35 36

2θ /°

the process with mass loss, a 0 % mass gain in the dis-
cussed temperature range (100–190 °C) is not necessarily
equivalent with the complete oxidation of magnetite. The
thermal stability of sample B was also studied at a higher
temperature: 60 °C. The evolution of TG curves (Fig. 4d)
evidences the fact that the oxidation process of magnetite is
practically absent after only 1 day of exposure of sample B
in air at 60 °C.
To better evidence the evolution in time of the different
iron oxide phases, we studied the changes in time of the
FTIR spectra of the studied powders. Due to the overlap-
ping of the characteristic bands of magnetite and maghe-
mite, we have resorted to derivative spectroscopy.
According to the literature [44, 45], the existence and
location of overlapped and hidden peaks can be found
by spectra deconvolution or by spectra differentiation
(derivative spectroscopy). The later method involves the
analysis of the FTIR spectrum derivatives. Differentia-
tion reveals details of slope change and rate of change
in the experimental spectrum which reveals the presence
of hidden and overlapped peaks [44]. For a symmetric
peak, the first derivative will cancel at peak maximum,
while the second derivative has its minimum [45]. In
order to evidence the presence of maghemite in the
system, we used both first and second FTIR spectra
derivatives.

123
1194 M. Stoia et al.

14000

110 days
12000

90 days
10000
60 days
Intensity/counts

8000 29 days

15 days
6000

3 days
4000
2 days

2000 1 day

initial
0
10 20 30 40 50 60 70 8035 36

2θ /°

Fig. 11 XRD patterns of sample H during storing in air at 25 °C

Fig. 12 XRD patterns of 6000

sample B during storing in
air at 60 °C
5000
5 days

4000
Intensity/a.u.

2 days
3000

2000
1 day

1000

initial
0
10 20 30 40 50 60 70 80 35 36

2θ /°

Figure 5 shows the evolution of FTIR spectra (Fig. 5a)
and of their first (Fig. 5b) and second derivatives (Fig. 5c)
for sample A. The asymmetry of the band with maximum
at 574 cm-1 suggests the presence of maghemite beside
magnetite in the initial sample A (Fig. 5a). In time, by
exposure to air (with oxidant effect on Fe(II) atoms from
surface), a shoulder appears around 620 cm-1, character-
istic to maghemite. This shoulder becomes a band after
60 days, and its intensity increases up to 110 days. The first
derivatives of the FTIR spectra (Fig. 5b) point out the
separation between the band at 570 cm-1 and the one at
620 cm-1, through the band located at 607 cm-1; practi-
cally the more intense this band is, the more clear the
separation between the two bands is. The second deriva-
tives of FTIR spectra (Fig. 5c) have minima located at the
same wavenumber as the maxima from the FTIR spectra,
but the separation between bands is clearer. The degree of
magnetite oxidation to maghemite can be appreciated (only
qualitatively in this study) through the band located around
630 cm-1. The ratio between the intensity of the band

123
Investigation of magnetite nanoparticles stability in air by thermal analysis and FTIR spectroscopy
Fig. 13 SEM images of samples A (a), B (b) and H (c) after storage
for 110 days in air at 25 °C
located at *630 cm-1 (characteristic to maghemite) and
of the one located at *560 cm-1 can be used as a tool for
the quantitative determination of magnetite/maghemite
mixture. It can be observed the significant change, espe-
cially in case of second derivative (Fig. 5c) after 1 day in
air exposure. One can notice that, despite the fact that the
mass gain due to magnetite oxidation disappeared after
15 days, the evolution of FTIR spectra shows that mag-
netite continues to transform into maghemite up to
90 days (the last two FTIR spectra and their derivatives
are similar).
In case of sample B (Fig. 6), the derivatives evidence
the fact that, in the initial sample, maghemite is almost
absent and its presence becomes significant only after
15 days and increases up to 60 days; the last two spectra
and derivatives are almost identical, so the process is sig-
nificantly slowed after 90 days. It is clear that in this case
the maghemite content in the final product (after 110 days)
is smaller in comparison with sample A.
The FTIR spectra of sample H (Fig. 7) clearly reveal
from the first moment the presence of maghemite phase,
beside the more evident goethite phase (bands at
1195
896 and 796 cm-1) and magnetite. In this particular case,
the evolution of FTIR spectra and of their first derivatives
is clearer in comparison with the second derivative, due to
the strong bands generated by goethite, which significantly
diminishes the intensity of maghemite band, making its
evolution less clear. In this case, as for sample B, the
changes from 90 to 110 days are small, suggesting the
stabilization of the final product.
The increase in storing temperature significantly
enhanced the oxidation process. Despite the TG curves of
sample B kept at 60 °C (Fig. 4d), which indicate that the
characteristic mass gain stopped after 1 day, the FTIR
spectra and their derivatives (Fig. 8) kept changing up to
the fifth day. In this case, the oxidation degree of magnetite
to maghemite is significantly higher, compared with the
case of sample B kept at 25 °C. This conclusion is sus-
tained especially by the FTIR spectra, where the band
located at 634 cm-1 significantly increases its intensity,
and by the second derivative, where the two bands
(570 and 630 cm-1) have close intensities. The advanced
oxidation of magnetite to maghemite after 1 day is evi-
denced by both the first and the second derivatives (much
evident for the later) of the FTIR spectra (Fig. 8b, c).
In contradiction to the FTIR spectra and their derivatives,
the XRD patterns exhibit a less visible change in time,
making the identification of both spinel phases (magnetite
and maghemite) more difficult. However, in all cases a shift
of diffraction maxima is observed in time for all samples
[Figs. 9–11, detail for (311) maxima], much visible in case
of sample B kept at 60 °C (Fig. 12). In case of sample H,
there is a very small shift in the position of the diffraction
peak corresponding to line (311), probably due to the lower
content of magnetite (in mixture with maghemite and goe-
thite) and the superposition of goethite maxima.
The increase in storage temperature from 25 to 60 °C, as
evidenced by TG and FTIR studies, significantly increases
the rate of oxidation. Thus, the main shift of (311) maxi-
mum takes place after only 1 day and then becomes
imperceptible.
SEM images of the synthesized powders, stored in air
for 110 days, show that all powders are formed by
nanoparticles with diameters up to 25 nm (Fig. 13a–c),
agglomerated in micrometrical aggregates. The powder B
obtained with benzylamine (Fig. 13b) has a more
homogenous morphology, with nanoparticles nearly
spherical, better defined. In case of sample H, obtained
with NaOH, the SEM image (Fig. 13c) evidences the
presence of two phases: one consisting in nearly spherical
nanoparticles up to 25 nm (probably maghemite) and one
consisting in rod-like particles with length up to 100 nm
and width up to 15 nm (probably goethite).
The magnetic behavior of the synthesized powders,
after oxidation during 110-day storage in air, at 25 °C, and
123
1196 M. Stoia et al.

75 75
(a) (b)
50 50

25 25

σ/emu g–1
σ/emu g–1

0 0

–25

–50 –50

–75 –75
–5 –4 –3 –2 –1 0 1 2 3 4 5 –5 –4 –3 –2 –1 0 1 2 3 4 5
H/kOe H/kOe
75 75
(c) (d)
50 50

25 25
σ/emu g–1

σ/emu g–1
0 0

–25 –25

–50 –50

–75 –75
–5 –4 –3 –2 –1 0 1 2 3 4 5 –5 –4 –3 –2 –1 0 1 2 3 4 5
H/kOe H/kOe

Fig. 14 Magnetization cycles of samples stored at 25 °C a A, b B and c H and of sample B, stored at 60 °C (d)

of the sample B stored in air at 60 °C, in external magnetic
field up to 5 kOe is shown in Fig. 14a–d. It is obvious that
the magnetic behavior tends to superparamagnetic one, but
all powders have coercivity between 200 and 400 Oe,
probably due to the polycrystalline nature of the nanopar-
ticles (not monodomenial particles) and also to the pres-
ence of at least two phases. Powders A (Fig. 14a) and B
(Fig. 14b), stored at 25 °C, have the same magnetization
at maximum magnetic field of 5 kOe, of about
62 emu g-1, characteristic to maghemite nanopowders
[4], as previously reported in the literature. Sample H,
stored in air, at 25 °C for 110 days, has a significantly
lower magnetization, of 40 emu g-1, due to the presence
of goethite in a significant proportion (45 %). The mag-
netic behavior of sample B stored in air at 60 °C for 5 days
is similar to the one of the same powders stored at 25 °C,
probably due to the same composition of the final powder
(mostly maghemite).
Conclusions
Magnetic iron oxides were prepared by precipitation of
Fe(II) hydroxide using different precipitation agents:
ammonia, benzylamine and sodium hydroxide, followed by
oxidation with the oxygen dissolved in water. Thermal
analysis, coupled with FTIR spectroscopy, has evidenced the
formation of a mixture of magnetite and maghemite, with a
higher content of magnetite in case of the powder synthe-
sized with benzylamine. When NaOH was used as precipi-
tant, goethite was obtained as secondary phase, beside the
spinel magnetic iron oxides. The stability in time during the
storage in air at 25 °C of the synthesized powders was
investigated by TG/DTG/DSC coupled thermal analysis,
FTIR spectroscopy and X-ray diffraction. Thermal analysis
evidenced the presence of magnetite in the powders based on
the oxidation process that occurs in the temperature range
100–190 °C. Due to the superposition of other endothermic
processes, the oxidation process could not be used for the
quantification of magnetite content. FTIR spectroscopy was
very useful especially in case of the second derivatives, to
evidence the presence and the increasing of maghemite
content in time. XRD technique evidenced the changing of
powders composition through the small shift of the diffrac-
tion maxima at higher 2-theta values. The powders obtained
were formed by micrometric aggregates of nanoparticles
with diameters up to 25 nm. No significant change in the
powders morphology occurred during the storage in air. The
magnetic behavior of the oxidized samples was character-
istic to maghemite nanopowders, with exception of the
powder obtained with sodium hydroxide, due to the presence
of non-magnetic goethite phase.

123
Investigation of magnetite nanoparticles stability in air by thermal analysis and FTIR spectroscopy
Magnetite stability clearly depends on the nature of the
precipitant and on the storing temperature. From the three
investigated precipitants, the most stable magnetite was
obtained by using benzylamine, while the most unstable was
obtained by using NaOH. The temperature increase signifi-
cantly decreases the stability of synthesized magnetite.
Of the three techniques used for the identification of
magnetite and maghemite in a mixture, the most accurate
information was provided by FTIR spectroscopy.
Acknowledgements This work was supported by a grant of the
Romanian National Authority for Scientific Research and Innovation,
CNCS–UEFISCDI, Project Number PN-II-RU-TE-2014-4-0514.
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