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Journal of Alloys and Compounds 420 (2006) 1519

Structural, magnetic and magnetocaloric effect in


double perovskite Ba2CrMo1xWxO6
A. Dhahri a , J. Dhahri a, , S. Zemni a , M. Oumezzine a , H. Vincent b
a Laboratoire Physico-Chimie Structurale, Departement de Physique, Faculte des Sciences de Monastir 5019, Tunisia
b Laboratoire des Materiaux et de Genie Physique, ENSPG, BP 46, 38402 Saint Martin dHeres Cedex, France

Received 26 September 2005; received in revised form 8 October 2005; accepted 18 October 2005
Available online 15 December 2005

Abstract
Magnetic refrigeration, an emerging new technology for cooling and gas liquefaction, needs magnetic materials with specific thermomagnetic
behavior. Depending on the thermodynamic cycle selected, the isothermal magnetic entropy change or the adiabatic temperature change upon field
application needs to be a preselected function of temperature. In double perovskite Ba2 CrMo1x Wx O6 (x = 0, 0.2 and 0.5) prepared by the solgel
method, the experimental results show the observation of a large magnetocaloric effect (MCE) near the Curie temperature TC which decreases with
the increasing of the substitution of Mo by W. The maximum of the magnetic entropy change peaks at the magnetic ordering temperature TC , and
a large magnetic entropy change (|SM | 1.6 J kg1 K1 ) is obtained at 285 K in the sample Ba2 CrMo0.5 W0.5 O6 under an applied magnetic field
of 10 kOe.
2005 Elsevier B.V. All rights reserved.

Keywords: Magnetic entropy; Double perovskite; Curie temperature; Magnetic refrigerants

1. Introduction alloys of rare earths with high total angular momentum quan-
tum number, which provided a comparatively large magnetic
It has been discovered that, in some of the mixed-valent entropy change at the Curie temperature (TC ) in the R2 Fe17
perovskite materials, a metalinsulator (MI) transition is accom- (R = Y, Pr) [5], such as Gd [6] and RAl2 (R = Er, Dy, Ho, etc.
panied by a ferromagnetic (FM) ordering transition [1,2]. When . . .) [7]. In particular, a giant magnetocaloric effect takes place in
a magnetic field is applied to this kind of material, the unpaired Fe49 Rh51 [8] and Gd5 Si2 Ge2 [9] at the first-order transition tem-
spins are aligned parallel to the field. Since the total entropy of perature. Recently the attention have been focused on perovskite
spins plus the lattice remains constant, the entropy is removed type ferromagnetic oxides and double perovskites which have
from the spin system and goes into the lattice, which lowers become a subject attracting a considerable amount of investiga-
the magnetic entropy and produces a net heat. On the contrary, tion due to the colossal magnetoresistance (CMR) [1015] and
when the field is removed from the magnetic sample, the spin large magnetocaloric (MC) effect near the second order tran-
tends to become random, which causes a net cooling. This is the sition temperature TC [16,17]. In this paper, we report on the
principle of the magnetic refrigeration, which has been attracted magnetocaloric effect of double perovskite Ba2 CrMo1x Wx O6
considerable interest due to its advantages over gas refrigeration (x = 0, 0.2 and 0.5) as a function of W concentration x, temper-
[3,4]. Therefore, the maximum of the magnetic entropy change ature T and applied field H.
in this kind of material always occurs around its magnetic order-
ing temperature (i.e. Curie temperature TC ). To explore magnetic 2. Experimental
entropy change SM at high tempetrature (T > 20 K), previous
studies mainly concentrated on intermetallic compounds and In order to obtain high purity and homogeneous powders double perovskite
Ba2 CrMo1x Wx O6 (x = 0, 0.2 and 0.5) were prepared by the solgel method
described as following: stoichiometric amount of Ba(NO3 )2 , Cr(NO3 )3 9H2 O,
(NH4 )6 Mo7 O24 4H2 O and H2 WO4 , with nominal purities > 99.9%, were
Corresponding author. Tel.: +216 73 500278; fax: +216 73 500280. dissolved in concentrated nitric acid resulting in a light solution. Afterwards,
E-mail address: jemai dhahri@yahoo.fr (J. Dhahri). citric acid and ethylene glycol were added in a ratio of 4 g citric acid to 1 ml

0925-8388/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2005.10.030
16 A. Dhahri et al. / Journal of Alloys and Compounds 420 (2006) 1519

ethylene glycol. The solution was heated and the excess nitric acid and water
were boiled off giving a brown gel. The gel was heated to give a brown powder.
This precursor was calcined at 973 K overnight. The remaining powder was cold
pressed to 5 kbar and sintered at 1173 K for 24 h with intermediate grindings. At
the final stage, the pellets were sintered at 1273 K for 5 h resulting in a ceramic
material under an Ar/H2 (5%) atmosphere. The process was repeated four times
in order to complete the reaction. It is noteworthy that in order to guarantee
a precise sample composition, the sintering conditions must be carefully
observed. Higher temperatures and/or longer sintering times could produce
different sample compositions because of the possibility of molybdenum oxide
evaporation.
The phase purity of the samples was confirmed by X-ray diffraction (Siemens
D5000 X-ray diffractometer, with monochromatized Cu K1 radiation). The
XRD data were also used for refining the lattice parameters by means of Rietveld
analysis [18] (using FULLPROF program software). The microstructure was
observed by scanning electron microscopy (SEM). The pictures were taken at
room temperature on a Philips XL30 equipped with a field emission gun at
15 kV. Magnetizations (M) versus temperature (T) and versus magnetic field
Fig. 2. Observed (solid red lines) and calculated (solid black lines) X-ray diffrac-
(H) were measured by a Foner magnetometer equipped with a superconducting
tion pattern for Ba2 CrMo1x Wx O6 (x = 0.5). Positions for the Bragg reflections
coil in magnetic field. Magnetization M(H) curves of samples were obtained
are marked by vertical bars. Differences between the observed and the calculated
in an isothermal regime under an applied magnetic field varying from 0 kOe to
intensities are shown at the bottom. For interpretation of the references to color
10 kOe. In the vicinity of the Curie temperature TC , the temperature step for
in this figure legend, the reader is referred to the web version of the article.
these curves is of 3 K or 5 K.

3. Results and discussion maximum (FWHM) and s is the FWHM of a standard silicon
sample [19]. The as-obtained D are 135 nm and 96 nm for the
The morphology and particle size of the series samples with x = 0 and 0.2, respectively. Obviously, the particle
Ba2 CrMo1x Wx O6 (x = 0, 0.2) are observed with SEM as sizes observed by SEM are several times larger than those cal-
shown in Fig. 1. The spherical particles can be clearly dis- culated by XRD, which indicates that each particle observed by
tinguished and all the observed particles connect with each SEM consists of several crystallized grains.
other. In addition, we can clearly observe that the grain size Fig. 2 shows the refinement of X-ray diffraction patterns
is different in the two samples (x = 0, 0.2) and estimated to be for the samples Ba2 CrMo1x Wx O6 (x = 0.5). The result of X-
mostly within (450300 nm). However, we can also calculate ray diffraction indicates that all samples are single-phase. No
the average grain size (D) from the XRD peaks using the traces of secondary phases were delectable, within the sensi-
Scherrer formula: tivity limits of the experiment (a few percent). The diffraction
0.9 peaks are indexed with respect to the cubic structure with space
D= , group Fm3m. The results of refinement are listed in Table 1. In
cos
Table 1, are also reported the residuals for the weighted pattern
where is the X-ray wavelength employed, the diffraction Rwp , the pattern Rp , the structure factor RF and the goodness of
angle for the most intense peak (104), and is defined as fit 2 . In double perovskite Ba2 CrMo1x Wx O6 (x = 0, 0.2 and
2 = m2 2 . Here, is the experimental full width at half
s m 0.5) cubic structure with space group Fm3m the (Mo,W)O6 and

Fig. 1. Typical scanning electron micrographs (SEM) of: (a) Ba2 CrMoO6 (x = 0) and (b) Ba2 CrMo0.8 W0.2 O6 (x = 0.2) granular samples.
A. Dhahri et al. / Journal of Alloys and Compounds 420 (2006) 1519 17

Table 1
Refined structural parameters for Ba2 CrMo1x Wx O6 (x = 0, 0.2 and 0.5) after
the Rietveld refinements of X-ray powder diffraction data at room temperature
Parameters Ba2 CrMo1x Wx O6 (Fm3m)

x=0 x = 0.2 x = 0.5

a (A) 8.0098 (2) 8.0131 (1) 8.0156 (3)


b (A)
c (A)
V (A3 ) 513.884 (2) 514.519 (1) 515.001 (3)
Ba (atm) (1/4 1/4 1/4)
B (A2 ) 1.03 (4) 0.897 (6) 0.954 (3)
Cr1 (atm) (0 0 0)
B (A2 ) 0.47 (6) 0.39 (5) 0.41 (2)
Cr2 (atm) (1/2 1/2 1/2)
B (A2 ) 0.29 (6) 0.50 (5) 0.46 (2)
(W/Mo)1 (atm) (1/2 1/2 1/2)
B (A2 ) 0.44 (5) 0.43 (5) 0.47 (2) Fig. 4. Variation of the cell parameter a and cell volume with x ratio for the
sample Ba2 CrMo1x Wx O6 (x = 0, 0.2 and 0.5).
(W/Mo)2 (atm) (0 0 0)
B (A2 ) 0.25 (3) 0.29 (2) 0.32 (1)
to remains in the same symmetry and space group. Only small
O (atm) (x 0 0)
x 0.2634 (5) 0.2534 (5) 0.2484 (3) changes in the refinement parameter are observed.
B (A2 ) 0.59 (4) 0.63 (3) 0.52 (3) Fig. 4 shows that the lattice parameter a and the unit cell
Rwp (%) 6.75 5.98 6.52
volume V increase monotonically with increasing W concen-
Rp (%) 5.11 4.89 5.12 tration. The increasing in the lattice constant and the unit cell
RF (%) 6.38 5.99 6.28 volume can be related to the larger ionic radius of W ion
5+ 6+ 5+ 6+
2 (%) 2.18 2.65 3.27 (rW = 0.62 A , rW = 0.6 A and rMo = 0.6 A , rMo = 0.59 A )
[22]. This was confirmed by the determination by Rietveld
refinement of (W,Mo) O distance calculated from the structural
CrO6 octahedra which they are ordered and alternate along the parameters (see Table 2). The W doping leads to slight change
three directions in the crystal structure in such away that each in the overage B-site change in the original cubic structure and
CrO6 octahedron is linked to six (Mo,W)O6 octahedra and vice adjust Cr O bond length that increases, on the other hand, the
versa for all structure. Fig. 3 shows the 3D view of cubic double distance (W,Mo) O decreases and Cr O (W,Mo) bond angle
perovskites. The substitution of Mo by W leads, the structure who remains constant. The temperature dependence of low-
field magnetization for the above-mentioned samples, shown
in Fig. 5, was measured in a wide range of temperature (from
100 K up to 350 K) in an applied field of 500 Oe, in order to
determine the transition temperature of these materials. The fer-
romagnetic ordering transition temperature TC defined as the
temperature corresponding to the inflection point of the M (T)
curve decreases from 335 K to 285 K.
The decrease of TC can be assigned to this evolution between
the relative size of the CrO6 octeadres and (W,Mo)O6 that has
the effect of decreasing the interaction of double exchange, and
therefore, to reinforce the character antiferromagnetic in the
samples when x increases. In Fig. 6, the dependence of the Curie
temperature TC and (W,Mo) O bond length on the concentration
of W is shown. The enlargement of the (W,Mo) O (along each

Table 2
Values of average distances and angle in Ba2 CrMo1x Wx O6
Ba2 CrW1x Mox O6 (Fm3m)

x=0 x = 0.2 x = 0.5

dCr O (A) 2.026 (3) 6 2.058 (3) 6 2.086 (4) 6


d(W,Mo) O (A) 2.011 (2) 6 1.995 (1) 6 1.965 (2) 6
Fig. 3. The crystal structure of the double perovskite Ba2 CrMo1x Wx O6 (cubic, Cr O (W,Mo) ( ) 180 180 180
s.g Fm3m).
18 A. Dhahri et al. / Journal of Alloys and Compounds 420 (2006) 1519

Fig. 7. Magnetization vs. applied magnetic field H, measured at different tem-


peratures, for the sample Ba2 CrMo1x Wx O6 (x = 0.5). The temperature step
is 5 K in the region from 250 K to 300 K and 25 K for the others temperature
regions.
Fig. 5. Temperature dependence of magnetization for the sample
Ba2 CrMo1x Wx O6 (x = 0, 0.2 and 0.5) at a magnetic field of 0.05 T.
From maxwells thermodynamic relation:
   
M S
direction of the (W,Mo)O6 octahedra) bond length is consistent = (2)
with an decrease in the Curie temperature TC . T H H T
The magnetization decreases slightly with small amounts of one can obtain the following expression:
W doped, which may ascribed to a increase of the anti-site  Hmax  
M
defects of Cr and (W,Mo) on the B-sites. The nature and origin SM (T, H) = SM (T, Hmax ) SM (T, 0) = dH
of the relation ship between the magnetization and the anti-sites 0 T H
defects is still a matter of debate in the literature [23,24]. Fig. 7 (3)
shows the magnetization versus the applied magnetic field, of where Hmax is the maximum external field. According to Eq. (3),
the sample Ba2 CrMo0.5 W0.5 O6, obtained at various tempera- the magnetic entropy change depends on the temperature gradi-
tures. In our experiments, the changing rate of the applied field ent of the magnetization and attains a maximum value around
(20 Oe/s) is slow enough to consider the M(H) process being Curie temperature TC , at which the magnetization decays most
performed in an isothermal process. rapidly.
The entropy change SM , which results from the spin order- In fact, the magnetic entropy change SM is often evaluated
ing (i.e. ferromagnetic ordering) and is induced by the variation by some numerical approximation methods. One way of approx-
of the applied magnetic field from 0 to Hmax is given by: imation is to directly use measurements of the MT curve under
 Hmax   different magnetic fields. In the case of small discrete field inter-
S
SH = dH (1) vals, SM can be approximated from Eq. (3) as:
H T  
  M   
0
M 1
SM = + Hi (4)
T Hi T Hi+1 2
i

where (M/T )Hi is the experimental value obtained from the


MT curve in magnetic field Hi . Another method is to use isother-
mal magnetization measurements at small discrete field and
temperature intervals, SM can be approximately from Eq. (3)
by:
 Mi Mi+1
SM = Hi (5)
Ti+1 Ti
i

where Mi and Mi + 1 are the magnetization values measured in a


field H, at temperature Ti and Ti + 1 , respectively.
In this article, we adopt the latter method to evalute the
entropy change associated with the applied field variation.
Fig. 6. Curie temperature TC and (W,Mo) O bond length as a function of W
In Fig. 8, we show the temperature dependence of magnetic
concentration of Ba2 CrMo1x Wx O6 . entropy change (|SM |) under an applied field of 10 kOe for
A. Dhahri et al. / Journal of Alloys and Compounds 420 (2006) 1519 19

temperature of SM , 285 K, 308 K and 335 K, are nearly the


same of the values of the Curie temperature TC extracted from
low-field magnetization data.

4. Conclusion

In this paper we studied structural, magnetiand magnetic


entropy changes in Ba2 CrMo1x Wx O6 (x = 0, 0.2 and 0.5). The
results show a large magnetic entropy change (SM ) upon an
application of a low and modest magnetic field around the Curie
temperature TC and suggest that the W5+ dopant in some double
perovskite favors the (MC) effect in this series. It is suggested
by the results that these materials can be used as the working
material in an active magnetic regenerative refrigerator.

Fig. 8. The temperature dependence of magnetic entropy change (|SM |) under References
an applied field of 10 kOe for Ba2 CrMo1x Wx O6 (x = 0, 0.2 and 0.5).
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