Entropy change linked to the magnetic field induced Morin transition in

Hematite nanoparticles
J. M. Pastor, J. I. Pérez-Landazábal, C. Gómez-Polo, V. Recarte, S. Larumbe et al.

Citation: Appl. Phys. Lett. 100, 063102 (2012); doi: 10.1063/1.3682084

View online: http://dx.doi.org/10.1063/1.3682084
View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v100/i6
Published by the American Institute of Physics.

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 APPLIED PHYSICS LETTERS 100, 063102 (2012)

Entropy change linked to the magnetic field induced Morin transition

in Hematite nanoparticles
J. M. Pastor,1,a) J. I. Pérez-Landazábal,1 C. Gómez-Polo,1 V. Recarte,1 S. Larumbe,1
R. Santamarta,2 M. Fernandes Silva,3 E. A. Gómez Pineda,3 A. A. Winkler Hechenleitner,3
and M. K. Lima3
1
Departamento de Fı́sica, Universidad Pública de Navarra, Campus de Arrosadı́a, 31006 Pamplona, Spain
2
Departament de Fı́sica, Universitat de les Illes Balears, Ctra. de Valldemossa, km 7.5,
07122 Palma de Mallorca, Spain
3
Departamento de Quı́mica, Universidade Estadual de Maringá, 87020-900 Maringá-PR, Brazil

(Received 31 August 2011; accepted 16 January 2012; published online 6 February 2012)
The most stable form of iron oxide is Hematite (a-Fe2O3), which has interesting electronic,
catalytic, and magnetic properties showing size dependent characteristics. At room temperature,
Hematite is weakly ferromagnetic with a rhombohedral corundum structure. Upon cooling, the
structure undergoes a first order spin reorientation, in which the net magnetic moment is lost. This
transition is called the Morin transition. In this work, the first order Morin transition has been
analyzed as a function of the temperature and applied magnetic field in Hematite nanoparticles.
The magnetization was measured in the temperature range of the transformation at different
applied magnetic fields to evaluate the entropy change linked to the Morin transition. The magnetic
field promotes a shift of the transformation temperature. The change of entropy has been estimated
on the basis of Clausius-Clapeyron type equation. V C 2012 American Institute of Physics.

[doi:10.1063/1.3682084]

Hematite is the most stable form of iron oxide (a-
Fe2O3). Its electronic, catalytic, and magnetic properties are
of increasing interest from the application point of view in
different fields.1 At room temperature, Hematite is weakly
ferromagnetic with a rhombohedral corundum structure
(Space group R3c).2 The magnetic moments are approxi-
mately perpendicular to the rhombohedral axis with a small
canting of the magnetic sublattices, giving a small net mag-
netic moment. Upon cooling, the material undergoes a first
order spin reorientation transition, the Morin transition. The
moments align antiferromagnetically along the rhombohe-
dral axis, and the net magnetic moment goes to zero. Morin
transition temperature, Tm , is around to 260 K in bulk materi-
als.3,4 However, Tm depends on the mean particle size, d.
When the size is smaller than 100 nm, Tm decreases
abruptly.5,6 This effect is due to the increase of the surface-
volume ratio of the particles, which yields to a lack of sym-
metry at nanometric scale. Therefore, at low temperature, the
spin disorder causes the misalignment of the antiferromag-
netic order. For nanoparticles smaller than 10 nm, the antifer-
romagnetic order does completely vanish.7
When a system undergoes a first order transformation,8,9
the behaviour of the total entropy of the system as a function
of the temperature shows a discontinuity linked to the trans-
formation entropy, DStr. Different calorimetric techniques
have been employed in order to obtain DStr experimentally.
Adiabatic Calorimetry10,11 and Differential Scanning Calo-
rimetry12 (DSC) are widely employed with the purpose of
obtaining specific heat of both single crystal and nanopar-
ticles of Hematite. Nevertheless, neither of these experimen-
tal techniques has been able to detect any anomaly
associated to the Morin transition because of the slight value
a)
Electronic mail: josemartin.pastor@unavarra.es.
of DStr. Thermal relaxation calorimetry13 (Physical Proper-
ties Measurement System, PPMS) posses high resolution
compared with previous ones techniques. Nevertheless,
PPMS is not a suitable technique in the case of first order
transitions because their hysteretic nature. However the
latent heat of the Morin transition, L, has been obtained
directly using a modified DSC14 (L ¼ 18 J kg1 at 261 K;
DStr ¼ 0.069 J kg1 K1). In this work, the field dependence
of the thermo-magnetization curves has been used to deter-
mine the entropy change linked to the first order Morin tran-
sition in Hematite nanoparticles. The application of a
magnetic field promotes a shift of the transformation temper-
ature.15,16 The indirect estimation of DStr can be accurately
evaluated on the basis of the Clausius-Clapeyron equation.
The nanoparticles of Hematite were elaborated by modi-
fied aqueous sol-gel method.17 Saturated aqueous metal ni-
trate solution was prepared and maintained at room
temperature under stirring for two hours. After that, it is
heated under vigorous stirring until total water evaporation.
The temperature was maintained at 250  C until the total
thermal degradation. The nanostructured material was
obtained after burning the precursor powder under air atmos-
phere at 400  C.
X-ray measurements were carried out on a Siemens
D-5000 powder diffractometer with monochromated Cu
Ka1 radiation (k ¼ 1.54056 Å). Reflection x-ray powder dif-
fraction data were collected from 10 to 90 in 2h. The Riet-
veld Method and the Fullprof18 program have been used to
analyze the x-ray spectra. Finally, small drops of solutions
containing nanoparticles were deposited in 3 mm copper
grids coated with carbon and formvar films and observed in
a Hitachi H600 transmission electron microscope (TEM)
operating at 100 kV. The temperature dependences of the
magnetization M(T)H at different applied magnetic fields, H,

0003-6951/2012/100(6)/063102/4/$30.00 100, 063102-1 C 2012 American Institute of Physics

V

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063102-2 Pastor et al.
FIG. 1. X-ray diffraction pattern measured at room temperature (black
Points) and the Rietveld refinement (full line) using the crystallographic
structure of the Hematite. The insets show an image and a selected area elec-
tron diffraction pattern of the sample obtained by TEM.
were determined using a Quantum Design MPMS XL-7
SQUID magnetometer.
Figure 1 shows the x-ray diffraction pattern measured at
room temperature (black Points) and the Rietveld refinement
(full line) using the crystallographic structure of the Hema-
tite. It has been determined that the sample is pure Hematite.
Fourier transform infrared spectroscopy has been also used
to check the absence of other phases. The mean diameter
size is 57 nm determined by Scherrer formula. As can be
appreciated in the micrograph obtained by TEM (see inset of
Fig. 1), nanoparticles have irregular shape. The size of the
nanoparticles from the image is similar to the obtained by
x-ray diffraction. Additionally, selected area electron diffrac-
tion patterns obtained from small agglomerations of nano-
particles (inset of Fig. 1), ranging from hundreds of
nanometers to several microns, show always the crystallinity
of these particles, thus confirming the results obtained by
x-ray diffraction of the powders.
In order to characterize the Morin transition tempera-
ture, Tm, the low field (H ¼ 50 Oe) magnetization, M, was
FIG. 2. Magnetization of Hematite nanoparticles under a 0.005 T magnetic
field measured during cooling (full points) and heating (empty points).
Downloaded 06 Feb 2012 to 200.201.110.16. Redistribution subject to AIP license or copyright; see http://apl.aip.org/about/rights_and_permissions
Appl. Phys. Lett. 100, 063102 (2012)
FIG. 3. Magnetization of Hematite nanoparticles for different applied mag-
netic fields: diamonds, 0 kOe; squares, 10 kOe; circles, 20 kOe; up triangle,
30 kOe; down triangle, 40 kOe; left triangle, 50 kOe; right triangle, 60 kOe.
measured between T ¼ 100 and 300 K (Fig. 2) during cooling
and heating. As it is expected for a first order transition, hys-
teretic effect appears in the transition. The transition temper-
ature, determined from the temperature at maximum dM/dT,
is Tm ¼ 235 K and 245 K in cooling and heating regimes,
respectively. The smaller magnetization of the low tempera-
ture phase is due to the antiferromagnetic alignment of the
magnetic moments along the rhombohedral axis.
Figure 3 shows the thermo-magnetization M(T)H curves
measured on heating for different applied fields from H ¼ 0
to 60 kOe in the temperature range where the Morin transi-
tion takes place. Regarding the magnetostructural transition,
M(T)H shows a similar behavior in the whole range of
applied magnetic fields, that is, an increase in magnetization
upon heating across the Morin transition. The magnetization
change during the transformation has been estimated
as DM ¼ 0.3 emu/g for the maximum applied field
(H ¼ 60 kOe). The shift of the Morin transition to lower tem-
peratures, as the applied magnetic field increases, indicates
that the magnetic field stabilizes the high temperature phase
with respect to the low temperature one. Thus, the Morin
transition can be induced by an external magnetic field in a
particular temperature range. For example at 224 K the sam-
ple is in the antiferromagnetic state at zero field but the
application of a 60 kOe leads to the weak ferromagnetic
phase (temperature marked in Fig. 3 with an arrow).
The isothermal entropy change DS induced by the ap-
plied magnetic field can be obtained by numerical integration
of the Maxwell relation from isothermal thermo-
magnetization curves M(T)H. According to classical thermo-
dynamics, the entropy change DSðT; HÞ can be indirectly
estimated by magnetic measurements using the following
expression:19
ðH  
@M
DSðT; HÞ ¼ SðT; HÞ  SðT; 0Þ ¼ lo dH: (1)
0 @T H
Therefore, positive values of DSðT; HÞ are expected when
the M increases with T for the full set of applied fields in the
range of temperatures around Tm (see Fig. 3). In the case that
063102-3 Pastor et al. Appl. Phys. Lett. 100, 063102 (2012)

FIG. 4. Entropy change DS for different maximum applied fields in the tem-
FIG. 5. Tm as a function of applied field. Points correspond to experimental
perature range of the Morin transition. The inset shows the entropy change
data and straight line to linear fit.
DS as a function of the applied fields at 224 K (maximum of DS).

the magnetic field strongly affects the transition temperature basis of Clausius-Clapeyron type equation. The equation is
but scarcely modifies the heat capacity of both phases,11 a expressed as
limiting value of the DS  DStr should be expected,9,20
dT DM
where DStr is the structural transformation entropy. Besides ¼ lo ; (2)
this, to directly correlate the maximum entropy change deter- dH DStr
mined by magnetic measurements with DStr, it should be
where DM is the difference in the magnetization between the
taken into account the temperature range where the complete
low temperature antiferromagnetic phase and the high tem-
phase change is induced by an external magnetic field.
perature ferromagnetic phase. Using the values determined
The evolution of DS as a function of temperature for dif-
in the previous results for DM ¼ 0.3 emu/g ¼ 0.3 Am2 kg1
ferent applied magnetic fields is plotted in Fig. 4. A maxi-
and DS ¼ 0.030 J kg1 K1, we obtain dTm/dH ¼ 1.0 K/kOe
mum entropy change DS ¼ 0.030 6 0.002 J/kg K is achieved
that agrees fairly well with the measured field dependence of
for fields above 60 kOe at temperatures around 224 K. This
the transition temperature.
value is below the reported DStr value linked to the Morin
In summary, the first order Morin transition has been an-
transition in bulk Hematite (DStr ¼ 0.069 J kg1 K1).14 This
alyzed as a function of the temperature and applied magnetic
discrepancy could be related to the surface effects since it is
field in Hematite nanoparticles. The Morin transition
possible that an external core in the nanoparticles could not
depends on the applied field, and then it can be induced by
undergo the spin reorientation transformation due to the ab-
an external magnetic field. The entropy change linked to the
sence of structural order and so would not contribute to the
Morin transition has been determined through the Magnetic
estimated DS value. A different origin for this discrepancy is
field phase change induction. The magnetic field promotes a
based on the dependence on the temperature of the net en-
shift of the transformation temperature (Tm) evaluated on the
tropy change linked to a first order metamagnetic transfor-
basis of Clausius-Clapeyron equation.
mation21 as the Morin transition. Due to the opposite sign of
the vibrational and magnetic contributions to the transforma- 1
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3
The increase of the entropy change, as a function of the J. F. Bengoa, A. M. Alvarez, A. E. Bianchi, G. Punte, R. E. Vandenberghe,
R. C. Mercader, and S. G. Marchetti, Mater. Chem. Phys. 123, 191 (2010).
applied magnetic field (inset in Fig. 4) for T < TM 4
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(T ¼ 224 K) can be explained taking into account the behav- Godinho, Phys. Rev. B 68, 212408 (2003).
5
ior of the entropy of the system as a function of temperature Ö. Özdemir, D. J. Dunlop, and T. S. Berquó, Geochem. Geophys. Geosyst.
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6
N. Amin and S. Arajs, Phys. Rev. B 35, 4810 (1985).
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10
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12
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Similar values have been previously reported (dTm/dH 13
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14
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