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
It has been discovered that, in some of the mixed-valent
perovskite materials, a metalinsulator (MI) transition is accom-
panied by a ferromagnetic (FM) ordering transition [1,2]. When
a magnetic field is applied to this kind of material, the unpaired
spins are aligned parallel to the field. Since the total entropy of
spins plus the lattice remains constant, the entropy is removed
from the spin system and goes into the lattice, which lowers
the magnetic entropy and produces a net heat. On the contrary,
when the field is removed from the magnetic sample, the spin
tends to become random, which causes a net cooling. This is the
principle of the magnetic refrigeration, which has been attracted
considerable interest due to its advantages over gas refrigeration
[3,4]. Therefore, the maximum of the magnetic entropy change
in this kind of material always occurs around its magnetic order-
ing temperature (i.e. Curie temperature TC ). To explore magnetic
entropy change
SM at high tempetrature (T > 20 K), previous
studies mainly concentrated on intermetallic compounds and
Corresponding author. Tel.: +216 73 500278; fax: +216 73 500280.
E-mail address: jemai dhahri@yahoo.fr (J. Dhahri).
alloys of rare earths with high total angular momentum quan-
tum number, which provided a comparatively large magnetic
entropy change at the Curie temperature (TC ) in the R2 Fe17
(R = Y, Pr) [5], such as Gd [6] and RAl2 (R = Er, Dy, Ho, etc.
. . .) [7]. In particular, a giant magnetocaloric effect takes place in
Fe49 Rh51 [8] and Gd5 Si2 Ge2 [9] at the first-order transition tem-
perature. Recently the attention have been focused on perovskite
type ferromagnetic oxides and double perovskites which have
become a subject attracting a considerable amount of investiga-
tion due to the colossal magnetoresistance (CMR) [1015] and
large magnetocaloric (MC) effect near the second order tran-
sition temperature TC [16,17]. In this paper, we report on the
magnetocaloric effect of double perovskite Ba2 CrMo1x Wx O6
(x = 0, 0.2 and 0.5) as a function of W concentration x, temper-
ature T and applied field H.
2. Experimental
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
dissolved in concentrated nitric acid resulting in a light solution. Afterwards,
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.
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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
The morphology and particle size of the series
Ba2 CrMo1x Wx O6 (x = 0, 0.2) are observed with SEM as
shown in Fig. 1. The spherical particles can be clearly dis-
tinguished and all the observed particles connect with each
other. In addition, we can clearly observe that the grain size
is different in the two samples (x = 0, 0.2) and estimated to be
mostly within (450300 nm). However, we can also calculate
the average grain size (D) from the XRD peaks using the
Scherrer formula:
0.9
D= , group Fm3m. The results of refinement are listed in Table 1. In
cos
where is the X-ray wavelength employed, the diffraction
angle for the most intense peak (104), and is defined as
2 = m2 2 . Here, is the experimental full width at half
s m
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
samples with x = 0 and 0.2, respectively. Obviously, the particle
sizes observed by SEM are several times larger than those cal-
culated by XRD, which indicates that each particle observed by
SEM consists of several crystallized grains.
Fig. 2 shows the refinement of X-ray diffraction patterns
for the samples Ba2 CrMo1x Wx O6 (x = 0.5). The result of X-
ray diffraction indicates that all samples are single-phase. No
traces of secondary phases were delectable, within the sensi-
tivity limits of the experiment (a few percent). The diffraction
peaks are indexed with respect to the cubic structure with space
Table 1, are also reported the residuals for the weighted pattern
Rwp , the pattern Rp , the structure factor RF and the goodness of
fit 2 . In double perovskite Ba2 CrMo1x Wx O6 (x = 0, 0.2 and
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

Fig. 6. Curie temperature TC and (W,Mo) O bond length as a function of W
concentration of Ba2 CrMo1x Wx O6 .
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.
In Fig. 8, we show the temperature dependence of magnetic
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).
[1] J. Fontcuberta, B. Martinez, A. Seffer, S. Pinol, J.L. Garcia, X. Obradors,
Table 3  max  Phys. Rev. Lett. 76 (1996) 11221125.
Curie temperature TC , the maximum magnetic entropy change 
SM  and a [2] S. Zemni, J.A. Dhahri, K. Cherif, J.E. Dhahri, M. Oumezzine, M.
magnetic field H, for several materials considered for application for magnetic Ghedira, H. Vincent, J. Solid State Chem. 177 (2004) 23872393.
refrigeration [3] H. Zhu, H. Song, Y.H. Zhang, Appl. Phys. Lett. 81 (2002) 34163418.
 max 
Material H (kOe) TC (K) 
SM  (J kg1 K1 ) Source [4] H. Oesterreicher, F.T. Parker, J. Appl. Phys. 55 (12) (1984) 43344338.
[5] K. Mandal, A. Yan, P. Kerschl, A. Handstein, O. Gutfleisch, K.H. Muller,
of data
J. Phys. D Appl. Phys. 37 (2004) 26282631.
Gd 15 293 3.25 [20] [6] M. Foldeaki, R. Chachine, T.K. Bose, J. Appl. Phys. 77 (7) (1995)
La0.67 Ca0.33 MnO3 15 260 1.50 [21] 35283537.
La0.60 Y0.07 Ca0.33 MnO3 15 260 0.85 [21] [7] T. Hashimoto, T. Kuzuhara, M. Sahashi, K. Inomata, A. Tomokiyo, H.
La0.14 Nd0.56 Sr0.3 MnO3 15 268 1.43 [17] Yayama, J. Appl. Phys. 62 (3873) (1987) 38733878.
Sr2 FeMo0.65 W0.35 O6 10 404 1.32 [16] [8] B. Raveau, A. Maignan, V. Caignaert, J. Solid State Chem. 117 (1995)
Ba2 CrW0.5 Mo0.5 O6 10 285 1.61 Present 424426.
work [9] V.K. Pecharsky, K.A. Gschneidner Jr., Phys. Rev. Lett. 78 (23) (1997)
Ba2 CrMo0.8 W0.2 O6 10 308 1.45 Present 44944497.
work [10] J.P. Zhou, R. Dass, H.Q. Yin, J.S. Zhou, L. Rabenberg, J.B. Goodenough,
Ba2 CrMoO6 10 335 1.26 Present J. Appl. Phys. 87 (9) (2000) 50375039.
work [11] H. Roder, J. Zang, A.R. Bishop, Phys. Rev. Lett. 76 (1996) 13561359.
[12] B. Vertruyen, R. Cloots, A. Rulmont, G. Dhalenne, M. Ausloos, J. Appl.
Phys. 90 (11) (2001) 56925697.
Ba2 CrMo1x Wx O6 (x = 0, 0.2 and 0.5). As expected from Eq. [13] P.G. Radaelli, G. Iannone, M. Marezio, H.Y. Hwang, S.-W. Cheong, J.D.
Jorgensen, D.N. Argyriou, Phys. Rev. B 56 (1997) 82658276.
(3), the peaks of the magnetic entropy changes of the three sam- [14] K. Cherif, J. Dhahri, E. Dhahri, M. Omezine, H. Vincent, J. Solid State
ples are around the Curie temperature TC . The maximum entropy Chem. 163 (2001) 466471.
change corresponding to a magnetic field variation of 10 kOe for [15] S. Zemni, J.A. Dhahri, K. Cherif, J. Dhahri, M. Oumezzine, M. Ghedira,
Ba2 CrMo0.5 W0.5 O6 is about 1.6 J kg1 K1 . To assess the appli- H. Vincent, J. Alloys Compd. 392 (2005) 5561.
cability of Ba2 Cr(Mo,W)O6 samples for magnetic refrigeration, [16] W. Zhong, W. Liu, X.L. Wu, N.J. Tang, W. Chen, C.T. Au, Y.W. Du,
Solid State Commun. 132 (2004) 157162.
the maximum |
SM | values determined in the present studies are [17] K. Cherif, S. Zemni, J.A. Dhahri, J. Dhahri, M. Omezine, M. Ghedira,
compared in Table 3 with those reported in literature for several H. Vincent, J. Alloys Compd. 396 (2005) 2933.
materials considered promising for such application. [18] H.M. Rietveld, J. Appl. Crystallogr. 2 (1969) 65.
Though the maximum |
SM | 1.6 J kg1 K1 for [19] A. Guinier, in: X. Dunod (Ed.), Theorie et Technique de la Radiocristal-
H = 10 kOe is about 50% of that of pure Gd metal, the lographie, third ed., 1964, p. 462.
[20] J.B. Goodenough, Phys. Rev. 100 (1955) 564.

SM distribution is much more uniform than that of pure Gd, [21] X.X. Zhang, J. Tejada, Y. Xin, G.F. Sun, K.W. Wong, X. Bohigas, Appl.
which is desirable for an Ericson-cycle magnetic refrigerator Phys. Lett. 69 (23) (1996) 35963598.
[25]. This broad distribution could be ascribed to a spread of [22] R.D. Schanom, Acta Crystallogr. A32 (1976) 751767.
the ferromagnetic transition temperature in different ferromag- [23] J. Navarro, J. Nogues, J.S. Munoz, J. Fontcuberta, Phys. Rev. B 67
netic clusters caused by the inhomogeneity of structure and (2003), 174416-1, 174416-6.
[24] C. Ritter, J. Blasco, L. Morellon, J.M. De Teresa, J. Garcia, M.R. Ibarra,
stoichiometry [26]. In comparison ith pure Gd metal [20], the J. Magn. Magn. Mater. 226 (2001) 10701072.
ceramic samples are much cheaper; their Curie temperature can [25] G.V. Brown, J. Appl. Phys. 47 (1976) 36733680.
be easily adjusted by tuning the doping concentration; they are [26] T.L. Phan, M.H. Phan, L.V. Bau, N.X. Phuc, S.C. Yu, J. Magn. Magn.
much more chemically stable than pure Gd metal. The peaks Mater. 290291 (2005) 10051008.