Journal of Alloys and Compounds 542 (2012) 241–247

Contents lists available at SciVerse ScienceDirect

Journal of Alloys and Compounds

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

A comparative study of nanosized iron oxide particles; magnetite (Fe3O4),

maghemite (c-Fe2O3) and hematite (a-Fe2O3), using ferromagnetic resonance
Musa Mutlu Can a,b,⇑, Mustafa Cosßkun c,d, Tezer Fırat c
a
Faculty of Engineering and Natural Sciences, Sabancı University, Tuzla, Istanbul 34956, Turkey
b
Nanotechnology Research and Application Center, Sabancı University, Tuzla, Istanbul 34956, Turkey
c
Physics Engineering Department, Engineering Faculty, Hacettepe University, Beytepe, Ankara 06800, Turkey
d
Ministry of Energy and Natural Resources, Ankara 06100, Turkey

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

Article history: We investigated intra/inter particle interactions in single domain size magnetite (Fe3O4), maghemite
Received 26 May 2012 (c-Fe2O3) and hematite (a-Fe2O3) iron oxide particles. The magnetic analyses were done using vibrating
Received in revised form 17 July 2012 sample magnetometer and magnetic resonance measurements that were taken from 5 to 300 K and from
Accepted 19 July 2012
120 to 300 K, respectively. The magnetic resonance analyses were done for the iron oxides, frozen under
Available online 27 July 2012
5000 G fields in glycerol matrix. By changing the temperature, a change in resonance field lines was
observed at each Fe3O4, c-Fe2O3 and a-Fe2O3 nanoparticles. However, the fits in resonant lines showed
Keywords:
that Landé g values (spectroscopic splitting factor) stayed stable with temperature decrease. The thermal
Magnetic resonance line symmetry
Intra and inter particle interactions
sensitivities that were determined from Landé g factors, revealed three dominant interactions on reso-
Iron oxide nanoparticles nant lines namely; the exchange coupling in between Fe2+, Fe3+ and O (g1 = 3.01 ± 0.08), Fe3+ centers
(1.88 ± 0.03 6 g2 6 2.02 ± 0.03, depending on iron oxide states) and flip flop of O ions in between ionic
states of Fe2+–O1 and Fe3+–O2 (2.35 ± 0.06 6 g3 6 2.44 ± 0.06, depending on iron oxide states).
Ó 2012 Elsevier B.V. All rights reserved.

1. Introduction however, has no periodic vacancies. The other difference is the

Iron compounds have attractive magnetic properties. However,
the high surface reactivity and oxidation in air atmosphere are the
important disadvantages for iron [1]. Thus, the oxidized states of
iron particles, Fe3O4, c-Fe2O3 and a-Fe2O3, are employed in techno-
logical applications to passivate the surface reactivity of iron [2].
The basic distinguishable properties of iron oxide phases are partic-
ular magnetic behavior originating from vacancies and valance
states of irons in sub-lattices [3]. The valance state of an iron ion
causes the oxygen amount constructed around the iron ion, and
the oxygen construction is the main reason of magnetic formation
as mentioned in previously studies [3,4]. Even though iron has fer-
romagnetic character, different oxide forms of iron do not exhibit
same magnetic characteristics. Fe3O4 and c-Fe2O3 present ferri-
magnetic behavior and the main difference between these two
structures [4–6] is that while Fe3O4 has Fe+2 and Fe3+ cations, c-
Fe2O3 has only Fe3+ cations and vacancies in their sub-lattices.
On the other hand, a-Fe2O3 exhibits the canted antiferromagnet-
ism [7]. Like c-Fe2O3, a-Fe2O3 has only one type cation, Fe3+,
⇑ Corresponding author at: Faculty of Engineering and Natural Sciences, Sabancı
University, Tuzla, Istanbul 34956, Turkey. Tel.: +90 533 929 0718; fax: +90 216 483
9550.
E-mail address: musamutlucan@gmail.com (M.M. Can).
crystal structures. While a-Fe2O3 has a rhombohedral crystal
structure, Fe3O4 and c-Fe2O3 have cubic cells [7]. Each formation
has different magnetic behavior [5,6,8–11] as a result of the intra
and inter particle interactions.
Reaching to the nanometer scale particle size, interactions be-
come effective factors in the formation of magnetic property
[11]. The decrease of particle size leads enlargement of domain size
and decrease the domain number in the particle. Compared to the
bulk states, the magnetic differences in nano sizes are the conse-
quence of the balance changes of effectiveness between inter and
intra particle interactions [6,12]. The increase of atom amount on
the surface in nano scale also causes magnetic phenomena origi-
nating from the enhanced numbers of surface spins. Consequently;
exchange interactions and spin canting become an effective at
both, inside the structure and on the surface [6,8,12].
This study was conducted to understand the origins of magnetic
behavior of Fe3O4 (23.0±0.6 nm), c-Fe2O3 (25.5±0.5 nm) and a-
Fe2O3 (53.7±0.6 nm) nanoparticles. Throughout the study, single
domain (SD) stated iron oxide nanoparticles were investigated.
The domain states of the particle at room temperature were found
by magnetization vs. temperature curves, and the Ferromagnetic
Resonance (FMR) measurements were employed for the magnetic
characterization. The significant difference of our calculations from
previously studies [13–15] was based on analyzing the resonance

0925-8388/$ - see front matter Ó 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2012.07.091
242 M.M. Can et al. / Journal of Alloys and Compounds 542 (2012) 241–247
lines as the combination of Fe+2, Fe3+ magnetic centers and the
couplings of these magnetic centers under mediation of O atoms.
The each resonance line was associated with Landé g values.
2. Experimental
The procedure employed in syntheses of Fe3O4, c-Fe2O3 and a-Fe2O3, nanopar-
ticles were explained in previous works [2,16,17]. The structural analyses were per-
formed by X-ray powder diffractometer (XRD) and transmission electron
microscopy (TEM) investigations. The XRD analyses of the samples were done by
Rigaku model diffractometer with CuKa radiation. TEM studies were used to deter-
mine the average size of the nanoparticles by using a JEOL 2000 FX microscope. The
acceleration voltage was kept at 200 kV.
Quantum Design Physical Properties Measurements System (PPMS) was used
for zero-field-cooled (ZFC) and field-cooled (FC) magnetization measurements.
ZFC and FC measurements were taken in the temperature interval from 5 to
300 K after cooling the samples to 5 K under 100 Oe field.
Magnetic resonance spectra were recorded using a Bruker EMX-131 ESR spec-
trometer with the following operation conditions; microwave frequency 9.6 GHz,
center field 3100 G, scan range 6000 G, modulation frequency 100 kHz, modulation
amplitude 2 G and scan time 3 min. Temperature dependent measurements were
carried out using a variable temperature control system (ER 411 VT) of the magnetic
resonance spectrometer in the range of 120 and 300 K.
3. Results and discussion
The accordance between the peak positions of XRD patterns and
ICDS cards of Fe3O4, c-Fe2O3 and a-Fe2O3 particles were demon-
strated in Fig. 1. As seen from the figure, the XRD patterns are in
coherence with ICDS cards of, pdf # 74–0748 (Fe3O4), pdf # 25–
1402 (c-Fe2O3) and pdf # 79–0007 (a-Fe2O3). Fe3O4 nanoparticles
(23.0 ± 0.6 nm) were obtained, using mechanical milling technique
[2], as a first step in order to distinguish the magnetic character of
the other oxide states of iron. Then, the c-Fe2O3 (25.5 ± 0.5 nm)
and a-Fe2O3 nanoparticles (53.7 ± 0.6 nm) were obtained by heat-
ing Fe3O4 nanoparticles up to 250 °C (under vacuum) and to 500 °C
(under air atmosphere), respectively. The particle size distribu-
tions, obtained from the TEM pictures, are shown in Fig. 2d–f
and given in Table 1.
After understanding the structure, the dominant domain states
in samples were revealed from ZFC and FC measurements, shown
in Fig. 3. A totally splitting in between 300 and 5 K temperature
interval was observed at each FC and ZFC curves. These splits dem-
onstrate the blocking magnetic moments along their anisotropy
directions because of not having enough thermal energy to rotate
freely. Thus, the dominant domain states cannot be super para-
magnetic (SPM). On the other hand, the particle sizes are so small
to be multi domain (MD) state. Consequently, the dominant do-
main states should be SD which is in line with the results given
in literature [18,19].
The oxide state dependent magnetization of iron was investi-
gated by resonance field versus temperature (HR) variation. The
Fig. 1. XRD patterns of Fe3O4, c-Fe2O3 and a-Fe2O3. Particles were indexed
according to the standard of ICDS Cards, 74–0748, 25–1402 and 79–0007 for
Fe3O4, c-Fe2O3 and a-Fe2O3, respectively.
each oxide phase, in single domain size, has specific magnetic
interactions and, thus, different HR (T) values. Unlike the other iron
oxides, the only negligible change in between HR(T) curves was ob-
served for a-Fe2O3 as shown in Fig. 4(a) and Table 1. This assigned
the independent intra and inter particle magnetic interactions,
dipolar and exchange [10,24], in a-Fe2O3 nanoparticles from tem-
perature. The interparticle interaction effect on magnetization of
a-Fe2O3 nanoparticles was shown in the previous work [20]. Thus,
intra interactions in iron oxide particles were only focused in this
study.
The investigation is based on the relation between non-sym-
metric resonance line shapes and the effect of intra particle inter-
actions on symmetry of resonance lines. The ratios of H1 (the
difference between the minimum point of dI/dH curve and HR) to
H2 (the difference between HR and the maximum point of dI/dH
curve) were calculated, shown in Fig. 4(b), to point out the symme-
try of the magnetic resonance lines. The sequential calculated val-
ues were attached to each other by lines in Fig. 4(b) to emphasize
the change in symmetries. The average symmetry ratios, in values
between 120 and 300 K, of Fe3O4, c-Fe2O3 and a-Fe2O3 particles
were calculated as 0.748 ± 0.009, 0.77 ± 0.01 and 0.93 ± 0.02,
respectively. Asymmetric MR lineshapes are the results of the
interactions between the sublattices and unequivalent moments
in the sites [21]. Two different sublattices, tetrahedral and octahe-
dral, are the origins of magnetic characters of the Fe3O4, c-Fe2O3
and a-Fe2O3 particles [22,23]. The magnetic formations are the
consequence of interactions with different valence states of iron
(Fe+2 and Fe+3) and Oxygen (O2 and O) atoms [14,21,24] in these
sites. The possible defects in lattice also cause a significant effect
on magnetization [25].
In order to understand the effectiveness of intraparticle interac-
tions on iron oxides, the particles were dispersed in glycerol ma-
trix. Then this mixture was cooled down to 120 K under 5000 G
field strength to freeze the magnetic moments with low thermal
fluctuations through the easy axis in order to control the magnetic
anisotropies. After cooling down to 120 K, the perpendicular (\)
and parallel (//) resonance lines to external field were measured
as shown in Fig. 5. A shift to high fields was observed for all HR(//
) values due to effectiveness of anisotropy fields in the particles
as shown in Eq. (1).
X
HT ¼ Ha þ Hd þ Hij þ Hintra particle interaction ð1Þ
j¼1;N
j–i
P
In this equation HT is the total effective field, j¼1;N Hij is the inter-
j–i
particle interaction (dipolar and exchange interactions) field, Hd is
the demagnetization field, and Ha is the anisotropy field [16,26–
28]. In addition, the intra particle interaction originating from
spin–spin and spin–orbit coupling between nearest neighboring
spins, Hintra particle interaction , is the other effective parameter on mag-
netic field for ferrite particles [29]. These interactions are also the
origin of the resonance line and, in addition, the gradient of each
interaction shapes the symmetry of lines as shown in Eq. (2) [30].
       
@H @H @H @H
DH ¼ DH 0 þ D/ þ DH i þ DV þ DS ð2Þ
@/ @Hi @V @S
The 1st, 2nd, 3rd, 4th and 5th terms in Eq. (2) show the interac-
tions related to the intrinsic linewidth, a spread in the crystalline
axes, magnetic inhomogeneity, variations in particle size and sur-
face spins, respectively [30]. These all also associate with the effec-
tive anisotropy of the particles and, thus, the effective anisotropy is
seen as the main reason of the line shape [31].
The anisotropy field was eliminated by taking the resonance
lines through the external field, and the demagnetization effect
was neglected. The inter particle interaction was not totally elim-
inated; however, dispersing in glycerol matrix should cause a
 M.M. Can et al. / Journal of Alloys and Compounds 542 (2012) 241–247 243

Fig. 2. TEM micrographs and log normal size distributions of (a), (d) Fe3O4, (b), (e) c-Fe2O3 and (c), (f) a-Fe2O3 particles, respectively.

Fig. 2. (continued)

Table 1
Particle size, coercive (Hc) field [2], remenance (MR) magnetization [2] and magnetic resonance values of Fe3O4, c-Fe2O3 and a-Fe2O3 nanoparticles.

Sample TEM figures VSM measurments FMR measurments

300 K 120 K 300 K Slopes of HR(T) curve from 300 to 120 K
Particle size (nm) HC(G) MR (emu/g) HR(G) HR(G)
Fe3O4 23.0 ± 0.6 167 12.4 2446 0.43 ± 0.03 0.43 ± 0.03
c-Fe2O3 25.5 ± 0.5 141 9.1 2610 0.36 ± 0.04 0.36 ± 0.04
a-Fe2O3 54 ± 5 229 1.3 2995 0.10 ± 0.03 0.10 ± 0.03

specific decrease at inter particle interaction field. The dipolar
interactions are not dominant in our particles due to dispersing
the particles in glycerol matrix which declined the dipolar interac-
tions due to enhancement of distances between particles [32]. The
calculations were done just by taking attention of the intraparticle
interaction fields. The resonant line measurements of Fe3O4, c-
Fe2O3 and a-Fe2O3 particles were shown on the Fig. 5(a–c), respec-
tively. Below the room temperature, the magnetic moment fluctu-
ation along the easy direction performed a decrease and the
consequences were seen as a shift in both resonance field values,
HR(//) to low fields and HR(//) to high fields. This result supports that
the orientation of all moments are through the cooling field which
behaving as an anisotropy axis.
The relation between the resonance fields, depending on cool-
ing directions, and uniaxial anisotropy field were correlated by
the Eq. (2) [33,34]. The angle dependent resonance fields (HR ðhÞ)
was also shown in Fig. 5(d) in order to observe the uniaxial anisot-
2
ropy fields at 120 K. The coherency of measured values to sin ðhÞ,
244 M.M. Can et al. / Journal of Alloys and Compounds 542 (2012) 241–247

although in thermally stable state there should not be Fe2+ ions in

c-Fe2O3 and a-Fe2O3 lattices, there is no reason of not forming a
flip-flop between two resonant forms of Fe3+O2 and Fe2+O as
mentioned in study of Sastry et al. [21]. That is why; the calcula-
tions were developed by adding the flip-flop in between Fe3+–
O2 and Fe2+–O resonant states. The resonant lines of c-Fe2O3
and a-Fe2O3 particles were fitted to both suggested lines, associ-
ated with the flip-flop resonant state and with the Fe3+ centers.
After reaching to the harmony of these two fits on resonant lines
of c-Fe2O3 and a-Fe2O3, the Landé g value calculations for Fe3O4
particles were repeated for three resonant lines. The flip-flop in be-
tween Fe3+–O2 and Fe2+–O resonant states was the additional
curve on calculations, which was not considered in the previous
study [17].
Landé g values were calculated using the relation g ¼ lxhH where
B
microwave frequency (x), Planck constant (h) and Bohr Magnetron
27
(lB) with values 9.6 GHz, 6.626  10 (erg. s) and 9.27  1021
(erg/G), respectively [37]. H is the external field that we used both
Fig. 3. Zero field cooled (ZFC) and field cooled (FC) magnetization per gram vs.
resonance field values, HR(\) and HR(//), in the study due to find the
temperature measurements at 100 Oe for (a) Fe3O4, (b) c-Fe2O3 and (c) a-Fe2O3. related g calculations.
The calculated Landé g values in temperature intervals of 120 K
and 240 K were demonstrated on Table 2 and the fitted curves
shown in Eq. (2), was revealed the uniaxial anisotropy in each iron were shown just for 120 K and for 240 K on Fig. 6(a) and (c) and
oxide. on Fig. 6(d) and (f), respectively. The results of the calculations
HR ðhÞ  HR ð0 Þ were shown for all particles of Fe3O4,c-Fe2O3 and a-Fe2O3 in the
2
¼ sin ðhÞ ð3Þ figures.
HR ð90 Þ  HR ð0 Þ
The agreement in between theoretical and calculated mean val-
On the other hand, the calculated differences in between HR(//) ues (in the temperature interval of 120 and 300 K) was emphasized
and HR(\) fields, relating to the anisotropy field of by typing them in bold in Table 2. As seen in Table 2, the calcula-
HA aðHR ð90 Þ  HR ð0 ÞÞ [31,32], for Fe3O4, c-Fe2O3 and a-Fe2O3 par- tions were extended to the whole resonant lines from 120 to 240 K
ticles were found to be 716 ± 10 G, 644 ± 10 G and 318 ± 10 G, until melting point of glycerol. Above the 240 K the frozen mag-
respectively. The high value can be considered as the result of netic moments disappeared by melting glycerol. The fittings of
the high anisotropy in a sample. Moreover, coercive field (Hc)
and remanence magnetization (MR) values, taken from reference
[2], of the particles are also demonstrated in Table 1. As it is seen,
the MR value of a-Fe2O3 is the smallest one and, the largest MR is
observed for Fe3O4. Comparatively, an opposite character was
found at Hc values, which a-Fe2O3 has bigger Hc values than
Fe3O4. The magnetic behaves of a-Fe2O3 nanoparticles were de-
picted on dominant surface effects, which were emphasized for
nano size antiferromagnetic particles in study of Zysler [12]. Fur-
thermore, the interparticle interaction effectiveness on magnetic
behave was also investigated for a-Fe2O3 nanoparticles in previous
study [18]. A slight spin canting (1 min of arc) out of plane is
known the reason of a small net magnetic moment in bulk size
a-Fe2O3 particles [12]. The results for iron oxide particles (accord-
ing to the calculated values from Eq. (2) and shown data in Table 1)
show that the higher anisotropy field also lead the higher rema-
nent magnetization in iron oxides.
The intra interactions in c-Fe2O3 and a-Fe2O3 particles were
determined by fitting the magnetic resonance spectra to two lines
as shown in Fig. 6(b) and (c), Fig. 6(e), 6(f). The analyses were done
for HR(//) in order to eliminate anisotropy effects from the calcula-
tions. These analyses were not in accordance with the previous
study for Fe3O4 particles [17]. The fitting processes and calculated
Landé g values, 2.01 and 2.78, in the previous study [17] were in
agreement with the other reported values for Fe3+ centers
(g = 2.0) [21,35] and for exchange coupling between Fe2+, Fe3+
and O (in between g = 2.4 and 2.8) [21,36], respectively. However,
the idea has to be improved by taking into account of the asymme-
try in resonant lines of c-Fe2O3 and a-Fe2O3 particles. The asym-
metry revealed that the Fe3+ centers and the exchange coupling
in between Fe2+, Fe3+ and O ions cannot be the only reasons as
the origins of these resonant lines. Since the fact that, there is no
Fe2+ ion in c-Fe2O3 and a-Fe2O3 particles and if just Fe3+ centers Fig. 4. (a) Resonance fields (HR) and (b) H1/H2 vs. temperature curves of Fe3O4, c-
are effective, the resonant lines should be symmetric. Furthermore, Fe2O3 and a-Fe2O3 nanoparticles.
 M.M. Can et al. / Journal of Alloys and Compounds 542 (2012) 241–247 245

Fig. 5. The perpendicular (\) and parallel (//) resonant lines at 120 K under 5000 G external field for (a) Fe3O4, (b) c-Fe2O3 (c) a-Fe2O3 particles, and (d) the angle dependent
resonant lines of Fe3O4, c-Fe2O3 and a-Fe2O3 particles.

Table 2
Theoretical and calculated Landé g factors of Fe3O4, c-Fe2O3 and a-Fe2O3 particles.

Landé g\ Values
Expected Theoretical values Calculated values The calculated
interactions mean values
Iron Temperature (K)
in
oxides
120 140 160 180 200 220 240 temperature
interval of
120–240 K
The 3.4 (due to localized Fe+2 Fe3O4 3.00 ± 0.05 3.02 ± 0.08 3.04 ± 0.08 3.04 ± 0.08 3.01 ± 0.08 3.01 ± 0.08 3.00 ± 0.08 3.02 ± 0.08
exchange ions) [34], 2.5817 (due to c-Fe2O3 – – – – – – – –
coupling in exchange coupling in a-Fe2O3 – – – – – – – –
between between Fe+2 and Fe+3
Fe+2 and with O1) [21]
Fe+3
The flip-flop In between 2.5 and Fe3O4 2.38 ± 0.04 2.41 ± 0.04 2.39 ± 0.04 2.39 ± 0.04 2.41 ± 0.04 2.39 ± 0.04 2.43 ± 0.04 2.40 ± 0.04
resonant 2.6 [21] c-Fe2O3 2.39 ± 0.05 2.35 ± 0.06 2.37 ± 0.05 2.36 ± 0.05 2.33 ± 0.06 2.35 ± 0.06 2.35 ± 0.06 2.36 ± 0.06
state in a-Fe2O3 2.43 ± 0.06 2.50 ± 0.06 2.49 ± 0.06 2.45 ± 0.06 2.43 ± 0.05 2.38 ± 0.06 2.40 ± 0.05 2.44 ± 0.06
between
Fe3+–O2 and
Fe2+–O
Fe+3 centers 1.8 [21], 2.0 Fe3O4 1.94 ± 0.06 1.95 ± 0.06 1.94 ± 0.06 1.93 ± 0.06 1.92 ± 0.06 1.93 ± 0.06 1.98 ± 0.06 1.94 ± 0.06
[19,36], 2.01 [34] c-Fe2O3 1.97 ± 0.04 2.01 ± 0.04q 2.02 ± 0.04 2.02 ± 0.03 2.02 ± 0.03 2.01 ± 0.03 2.02 ± 0.03 2.01 ± 0.03
a-Fe2O3 1.89 ± 0.03 1.88 ± 0.03 1.88 ± 0.03 1.88 ± 0.03 1.88 ± 0.03 1.88 ± 0.03 1.88 ± 0.03 1.88 ± 0.03

the resonance curves were constructed taking into account of the
suggested origins of the possible contributions, namely; the ex-
change coupling in between Fe+2 and Fe+3, the flip-flop in between
Fe3+–O2 and Fe2+–O resonant states, and the Fe+3 centers. The
calculations on the resonance curves were carried out for these
three contributions, as shown in the Table 2.
As expected, the effectiveness of the exchange coupling in be-
tween Fe+2 and Fe+3 was not observed for c-Fe2O3 and a-Fe2O3 par-
ticles. The coherence between the measured values and the fittings
were observed for each resonance line. It is known that, the Landé g
value of localized Fe+2 ions [35] at around 3.4 and coupling with Fe+3
ions under mediation of cationic state of O atoms cause a decrease of
246 M.M. Can et al. / Journal of Alloys and Compounds 542 (2012) 241–247

Fig. 6. The fitted magnetic resonance lines, taken under 5000 G, at 120 K for (a) Fe3O4, (b) c-Fe2O3, (c) a-Fe2O3 particles and at 240 K for, (d) Fe3O4, (e) c-Fe2O3 and (f) a-Fe2O3
particles.

this value down to 2.58 [21]. Since the calculated g = 3.01 ± 0.08 val-
ues were in between these two g values, the values can be attributed
to the exchange coupling in between Fe+2 and Fe+3 ions.
The calculated g values were also shown on figures from Fig.
6(a) to Fig. 6(f). As seen from these figures, temperature variation
does not make significant changes at the Landé g values. However,
dominancy of flip-flop in between Fe3+–O2 and Fe2+–O resonant
states (defined by ‘‘g2 related intensity’’) at high temperatures was
realized due to increase in intensities of the associated fits in res-
onant lines as shown in Fig. 7(a). The calculations were done until
to the melting point of glycerol, 240 K. After melting point, orien-
tations of magnetic moment through the external field disap-
peared and no shift was observed in between both lines, parallel
and perpendicular lines to external field.
4. Conclusion
Consequently, the magnetic behavior of SD sized Fe3O4, c-Fe2O3
and a-Fe2O3 nanoparticles were investigated by taking attention
intra particle interactions. The magnetic formations in both sites,
tetrahedral and octahedral symmetries, of Fe3O4 nano particles
constructed from nonequivalent and different type cations. How-
ever, for a-Fe2O3 and c-Fe2O3, the asymmetry or symmetry can
be the results of non-equivalency of the magnetic moment of the
same cations of each sub lattice [4–6,8]. In addition, the Landé g
values were found to be independent of the temperature. The only
change was found in the intensities of fit curves. While the domi-
nancy of Fe+3 centers was found on magnetization at low temper-
atures, the increase of temperature causes an enhancement of the
 M.M. Can et al. / Journal of Alloys and Compounds 542 (2012) 241–247
Fig. 7. Normalized FMR absorption intensity, related to the Landé g factors, change in temperature interval of 120 and 240 K.
efficiency of flip-flop resonant states in between Fe3+–O2 and
Fe2+–O on magnetization of the iron oxides.
Acknowledgment
This work was supported by ‘‘The Scientific and Technical Re-
_
search Council of Turkey-TUBITAK’’, No. 104T322. The authors
thank to Prof. Dr. Mustafa Korkmaz for his guidance during the
magnetic resonance measurements.
References
[1] R. Kalyanaraman, S. Yoo, M.S. Krupashankara, T.S. Sudarshan, R.J. Dowding,
Nanostruct. Mater. 10 (8) (1998) 1379.
[2] M.M. Can, S. Özcan, T. Fırat, Phys. Stat. Sol. C 3 (5) (2006) 1271.
[3] R. Zboril, L. Machala, M. Mashala, V. Sharma, Crys. Growth Des. 4 (6) (2004)
1317.
[4] T. Belin, N. Guidue-Millot, T. Caillot, D. Aymes, J.C. Niepce, J. Solid State Chem.
163 (2002) 459.
[5] H. Kojima, K. Hanada, IEEE Trans. Magn. MAG-16 (1) (1980) 11.
[6] M.P. Morales, C.J. Serna, F. Bodker, S. Morup, J. Phys. Condens. Mater. 9 (1997)
5461.
[7] N. Randrianantoandro, A.M. Mercier, M. Hervieu, J.M. Greneche, Mater. Lett. 47
(2001) 150.
[8] M.P. Morales, S. Veintemillas-Verdaguer, M.I. Montero, C.J. Serna, Chem. Mater.
11 (1999) 3058.
[9] M. Vasquez-Mansilla, R.D. Zysler, C. Arciprete, M.I. Dimitrijewits, C. Saragovi,
J.M. Greneche, J. Magn. Magn. Mater. 204 (1999) 29.
[10] S. Morup, C. Frandsen, F. Bodker, S.N. Klausen, K. Lefmann, P.-A. Lindgard, M.F.
Hansen, Hyper. Inter. 144/145 (2002) 347.
[11] Ö. Özdemir, D.J. Dunlop, B.M. Moskowitz, Earth Planet. Sci. Lett. 194 (2002)
343.
[12] R.D. Zysler, M.V. Mansilla, D. Fiorani, Eur. Phys. J. B 41 (2004) 171.
[13] L.F. Gamarra, W.M. Pontuschka, J. Mamani, D.R. Cornejo, T.R. Oliveira, E.D.
Vieira, A.J. Costa-Filho, A. Amaro Jr., J. Phys. Condens. Mater. 21 (2009) 115104.
247
[14] S.K. Gupta, R.P. Pant, M. Arora, Indian J. Eng. Mater. Sci. 11 (2004) 305.
[15] Yu.A. Koksharov, S.P. Gubin, I.D. Kosobudsky, G.Yu. Yurkov, D.A. Pankratov, L.A.
Ponomarenko, M.G. Mikheev, M. Beltran, Y. Khodorkovsky, A.M. Tishin, Phys.
Rev. B 63 (2000) 012407.
[16] M.M. Can, S. Ozcan, A. Ceylan, T. Firat, Mater. Sci. Eng. B 172 (2010) 72.
[17] M.M. Can, M. Coskun, T. Firat, J. Nanopart. Res. 13 (2011) 5497.
[18] A.R. Muxworthy, D.J. Dunlop, Earth Planet. Sci. Lett. 203 (2002) 369.
[19] O. Ozdemir, D.J. Dunlop, Geophys. Res. Lett. 29 (18) (2002) 24.
[20] M.M. Can, T. Fırat, S. Ozcan, Phys. B 406 (2011) 2483.
[21] M.D. Sastry, Y.C. Nagar, B. Bhushan, K.P. Mishra, V. Balaram, A.K. Singhvi, J.
Phys. Condens. Mater. 20 (2008) 025224.
[22] R. Grau-Crespo, A.Y. Al-Baitai, I. Saadoune, N.H. De Leeuw, J. Phys. Condens.
Mater. 22 (2010) 255401.
[23] M.J. Benitez, D. Mishra, P. Szary, G.A.B. Confalonieri, M. Feyen, A.H. Lu, L.
Agudo, G. Eggeler, O. Petracic, H. Zabel, J. Phys. Condens. Mater. 23 (2011)
126003.
[24] F.X. Redl, C.T. Black, G.C. Papaefthymiou, R.L. Sandstrom, M. Yin, H. Zeng, C.B.
Murray, S.P. O’Brien, J. Am. Chem. Soc. 126 (2004) 14583.
[25] D.V. Dimitrov, G.C. Hadjipanayis, V. Papaefthymiou, A. Simopoulos, J. Vac. Sci.
Technol. A: Vac. Surf. Films 15 (3) (1997) 1473.
[26] K. Nagata, A. Ishihara, J. Magn. Magn. Mater. 104-107 (1992) 1571.
[27] E. De Biasi, C.A. Ramos, R.D. Zysler, J. Magn. Magn. Mater. 262 (2003) 235.
[28] M. Xu, C.R.H. Bahl, C. Frandsen, S. Morup, J. Colloid. Interf. Sci. 279 (2004) 132.
[29] H.B. Callen, E. Pittelli, Phys. Rev. B 119 (5) (1960) 1523–1531.
[30] D.S. Schmool, R. Rocha, J.B. Sousa, J.A.M. Santos, G. Kakazei, J. Magn. Magn.
Mater. 300 (2006) e331–e334.
[31] A.A. Bush, Y.K. Fetisov, K.E. Kamentsev, V.F. Meshcheryakov, G. Srinivasan, J.
Magn. Magn. Mater. 258-259 (2003) 45–47.
[32] C.J. Bae, Y. Hwang, J. Park, K. An, Y. Lee, J. Lee, T. Hyeon, J.G. Park, J. Magn. Magn.
Mater. 310 (2007) E806–E808.
[33] F. Gazeau, J.C. Bacri, F. Gendron, R. Perzynski, Y.L. Raikher, V.I. Stepanov, E.
Dubois, J. Magn. Magn. Mater. 186 (1998) 175.
[34] R.V. Upadhyay, D. Srinivas, R.V. Mehta, J. Magn. Magn. Mater. 214 (2000) 105.
[35] M. Tovar, M.T. Causa, A. Butera, J. Navarro, B. Martinez, J. Fontcuberta, M.C.G.
Passeggi, Phys. Rev. B 66 (2002) 024409.
[36] C.N. Marin, I. Malaescu, V. Socoliuc, J. Optoelectron. Adv. Mater. 5 (1) (2003)
227.
[37] A.V. Kessenikh, Physics – Uspekhi. 52 (7) (2009) 695.