Journal of Magnetism and Magnetic Materials 381 (2015) 215–219

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Journal of Magnetism and Magnetic Materials

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

Preparation of nanostructured La0.7Ca0.3
xBaxMnO3 ceramics by a

combined sol–gel and spark plasma sintering route and resulting
magnetocaloric properties
F. Ayadi a,b, Y. Regaieg a,b, W. Cheikhrouhou-Koubaa b, M. Koubaa b, A. Cheikhrouhou b,
H. Lecoq a, S. Nowak a, S. Ammar a, L. Sicard a,n
a
Université Paris Diderot, Sorbonne Paris Cité, ITODYS, UMR 7086 CNRS, 15 rue J.-A. de Baïf, 75205 Paris Cedex 13, France
b
Faculté des Sciences de Sfax, Université de Sfax, LPM, B.P 1171, 3000 Sfax, Tunisia

art ic l e i nf o a b s t r a c t

Article history: This work proposes an original, easy to achieve and inexpensive route to synthesize manganite ceramics
Received 9 July 2014 for magnetic refrigeration, combining sol–gel chemistry to Spark Plasma Sintering (SPS). The target
Received in revised form La0.7Ca0.3
xBaxMnO3 (x ¼ 0, 0.1, 0.2) compounds are obtained as single phases which crystallize in the
26 November 2014
orthorhombic structure (Pnma space group). SPS allows a quick sintering at a relatively low temperature
Accepted 16 December 2014
Available online 17 December 2014
(700 °C in this work) compared to the conventional solid state method (Z 1100 °C), leading to densified
ultrafine grained pellets (85% of compactness). Magnetic studies show that Ba substitution does not
Keywords: affect significantly the relative cooling power (RCP) of these manganites, while it increases their Curie
p-Doped manganite temperature (TC) by several tens of degrees. Typically, RCP values ranging between 267 and 270 J/kg (for a
Sol–gel
magnetic field change of 5 T) and TC between 205 and 245 K were measured when x was increased from
Spark Plasma Sintering
0 to 0.2, respectively. These results combined to the fact that the synthesis route is economically ad-
Nanostructured ceramic
Magnetocaloric properties vantageous makes the obtained ceramics interesting as active refrigerants for magnetic refrigeration
technology below room temperature.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction can be tuned from low temperature to near room temperature,

acting only on the chemical composition of these ceramics, which
Manganites of formula Ln1
xXxMnO3 (Ln: trivalent rare-earth is beneficial for magnetic refrigeration.
ion; X: divalent alkaline-earth ion) with the perovskite structure These materials are mainly prepared by the well-known solid
have been extensively studied over the last fifteen years regarding state route. This method is considered as a simple technique to
their various physical properties which can be used for a wide fabricate complex solid solution due to its easy-to-achieve tech-
variety of applications [1–6]. A large magnetocaloric effect (MCE), nological procedure. Nevertheless, it requires very high synthe-
which consists of an important change of temperature of an sizing temperature (4 1100 °C) and a very long heating time
adiabatically isolated system induced by the variation of an ex- (several days) which is, economically speaking, highly time and
ternal magnetic field, has been observed and extensively studied energy consuming. In this context, it is still interesting to develop
in these materials [7–9]. Although the maximum of entropy alternative synthesis and shaping route to produce these com-
change in these ceramic materials is smaller than that in the most pounds at lower cost. Pechini (sol–gel) process appears quite
naturally as a smart method for such a purpose if it can be com-
conspicuous magnetocaloric material Gd5Si2Ge2 [10], they remain
bined to a low temperature sintering technique.
still convenient to use in magnetic refrigeration technology since
Sol–gel chemistry has been extensively used these last years
they are easy to prepare and exhibit higher chemical stability.
[11–13], to produce pure and highly chemically homogeneous
Another important feature in such perovskite oxides is that they
nanopowders at relatively low temperatures (between 300 and
are quite suitable for carrier-doping (filling control) in their crys-
600 °C). Coupled to Spark Plasma Sintering (SPS), which is known
tallographic A-site since their structure is very robust against
as a sintering route operating with very high heating rates (as high
chemical modification. Therefore, a large magnetic entropy change as 100 °C min
1), at relatively low temperature and within short
times [14–16], it may retain all its advantages. Consequently, we
n
Corresponding author. decided to combine sol–gel chemistry and SPS technique to pro-
E-mail address: [email protected] (L. Sicard). duce pure, dense and ultrafine grained ceramics. As sol–gel

http://dx.doi.org/10.1016/j.jmmm.2014.12.047
0304-8853/& 2014 Elsevier B.V. All rights reserved.
216 F. Ayadi et al. / Journal of Magnetism and Magnetic Materials 381 (2015) 215–219

chemistry allows obtaining most mixed oxide gels and these gels
are highly reactive upon thermal treatment, this type of coupled
preparation technique can be been extended for the preparation of
numerous oxides.
In this paper we describe the optimized material processing
conditions to produce these La0.7Ca0.3
xBaxMnO3(x¼ 0, 0.1, 0.2)
manganites and we investigate their magnetic and magnetocaloric
properties in relation with their chemical composition, micro-
structure and processing conditions.

2. Materials and methods

2.1. Synthesis

La0.7Ca0.3
xBaxMnO3 samples (x ¼0, 0.1 and 0.2) were synthe-

sized by a two steps method. In the first step, stoichiometric
amounts of La2O3 (Sigma-Aldrich, 99.9%), CaCO3 (Sigma-Aldrich, Fig. 1. XRD patterns of a representative sample, namely x¼ 0, of the
Z99.0%), BaO (Sigma-Aldrich, 97.0%) and MnO2 (Sigma-Aldrich, La0.7Ca0.3
xBaxMnO3 solid solution (a) as-produced by the Pechini method,
Z99.99%) were dissolved in nitric acid. Citric acid (CA, Sigma-Al- (b) annealed at 500 °C in air and (c) sintered by SPS at 700 °C.

drich, 99%) and ethylene glycol (EG, Acros, 99%) were added to the
previous solution with the total metal:CA:EG molar ratio of 1:5:5. is still required. We decided to use the annealed powders at 500 °C
The resulting solution was left evaporating at 130 °C until a viscous as the starting materials for the SPS treatment. Without this cau-
gel-like product was formed and then subsequently dried by a tion, the removal of a large amount of gases during the SPS heating
slow heating in air up to 300 °C and annealed at 500 °C for 1 h in cycle may result in an explosion of the die. Different assays were
air. In the second step, the obtained powder (typical batch of 0.9 g) then performed to determine the best operating SPS conditions.
was introduced in a graphite die (Ø 8 mm) and enclosed between Fig. 2 displays the temperature profile, T, and the displacement
two conductive graphite punches. The whole reacting system was speed of punches, dz/dt, as a function of time, t, on a re-
placed into the SPS machine (Dr. Sinter 515S Syntex) and main- presentative sample of the studied manganite series. Any accident
tained under vacuum. An uniaxial pressure of 100 MPa was then in the dz/dt versus t plot is significant of reactions or sintering
applied and DC pulses were delivered to the die through the two events. The pressure was also recorded at the same time as gas
punches to rise rapidly the temperature up to a maximum of release is indicative of some reactions (desorptions, dehydroxyla-
700 °C (up to about 100 °C/min), as previously described [17]. tions, decarbonatations, …). A first outgassing is observed around
25 °C. It is attributed to the removal of adsorbed species. A second
2.2. Characterization one, between 400 °C and 600 °C is attributed to the total decom-
position of the intermediate solid and the formation of the man-
The X-ray diffraction (XRD) patterns of the produced powders ganite phase simultaneously with its consolidation. During the
and pellets were recorded on an Empyrean Panalytical dif- plateau at 700 °C, we did not observe significant punches dis-
fractometer equipped with a Cu-Kα anode (λ ¼ 1.5418 Å) in the 2θ placement, suggesting that only grain growth occurs during this
range 10°–90° using a step size of 0.0262°. Rietveld analysis was step. The XRD pattern recorded on the resulting pellets is given in
performed using FULLPROF software [18] to refine the cell para- Fig. 1c. It is characteristic of a well crystallized orthorhombic
meters of the obtained phases. manganite (Pnma space group) as confirmed by Rietveld analysis
The global chemical composition was determined by in- (see Supporting information). All the samples adopt the same
ductively coupled plasma mass spectrometry (ICPMS) at Vernaison structure, whatever their nominal Barium content. The refined
CNRS facilities and the Mn4 þ /Mn3 þ ratio by iodometric titration structural parameters are gathered in Table 1. A rapid overview of
[19]. the obtained structural results evidences a net increase of the unit
Scanning Electron Microscopy (SEM) was carried out using a cell volume with the Barium composition increase (Fig. 3), in
Supra40 ZEISS FEG-SEM microscope equipped with an In Lens agreement with the increase of the average ionic radius of the
detector. They were collected with low voltage (5 kV) at different
magnifications. Besides, the density of the as-produced pellets was
measured with a Micromeritics AccuPyc 1330 helium pycnometer.
Finally, magnetization measurements versus temperature and
magnetic field in the range 10–350 K and 0–5 T, respectively, were
carried out using a XL QUANTUM DESIGN SQUID magnetometer.

3. Results and discussion

3.1. Structural and microstructural analysis

All the Pechini-made powders consist of poorly crystallized

solids with some impurities (Fig. 1a). An annealing at 500 °C im-
proves their crystallinity: the XRD patterns match then fairly well
with those of the pure desired manganite structures (Fig. 1b). A
broad peak subsists around 30° indicating that the crystallization Fig. 2. Furnace temperature (left axis) and displacement speed of punches (right
is not fully achieved and that an annealing at a higher temperature axis) as a function of time during the SPS treatment.
 F. Ayadi et al. / Journal of Magnetism and Magnetic Materials 381 (2015) 215–219 217

Table 1
Refined structural parameters of the whole La0.7Ca0.3
xBaxMnO3 ceramic solid
solution.

x¼ 0 x¼ 0.1 x ¼0.2
Space group Pnma Pnma Pnma

a (Å) 5.476(5) 5.475(1) 5.478(1)

b (Å) 7.761(5) 7.767(1) 7.771(1)
c (Å) 5.472(4) 5.471(5) 5.473(1)
V (Å3) 232.591 232.646 232.983
〈Mn–O〉 (Å) 1.9844(9) 1.9772(7) 1.9661
〈Mn–O–Mn〉 (°) 159.253 159.737 160.687
χ2 (%) 1.29 1.330 1.42
〈rA〉 (Å) 1.354 1.381 1.408
s2nn (Å2) 8.4  10
5 5.9  10
3 1.02  10
2
Crystallite size (nm) 15 21 18

nn
Cationic disorder.

Fig. 3. Unit cell volume versus 〈rA〉 for the La0.7Ca0.3
xBaxMnO3 x¼ 0, 0.1 and
0.2 ceramics.

perovskite A-site in which Ba2 þ cations substitute Ca2 þ ones

(r(Ba2 þ )¼1.61 Å while r(Ca2 þ )¼ 1.34 Å [20]), confirming the in-
corporation of Ba ions and the formation of the desired solid
solution.
Besides, the La/Mn, Ca/Mn and Ba/Mn atomic ratios determined
by ICPMS analysis were used to determine the exact formula of the
prepared compounds (Table 2). They were found to be very close
to the expected values. The exact oxidation state of the manganese
ions was also determined by iodometric titration in order to
evaluate any oxygen non-stoichiometry in these samples. Indeed
these measurements should permit estimating Δ and y, the stoi-
chiometric coefficients of Mn4 þ and O2
atomic contents in the Fig. 4. SEM images of the La0.7Ca0.3
xBaxMnO3 (a) x ¼0, (b) 0.1 and (c) 0.2 ceramics.
La0.7Ca0.3
xBax(Mn13+− ΔMn 4Δ+ )Oy solid solution. The obtained results
are summarized in Table 2 for all the studied samples. They in- graphite die under vacuum, i.e. reductive conditions [21]. Such a
dicate a slightly lower quantity of tetravalent manganese species feature was already observed on previously SPS-made manganites
compared to what was expected, which indicates a slight defi- [17].
ciency in oxygen (Δ E2.965 instead of 3.000). Moreover, the The microstructure of the studied samples was also observed
oxygen vacancy concentration is constant, whatever the Ba com- by SEM. The recorded images (Fig. 4) show polydisperse nan-
position, suggesting that the observed non-stoichiometry is ometer-sized grains with an average diameter which decreases
mainly due to the sintering conditions, namely heating in a when the Ba content increases (63, 52, and 44 nm for x¼ 0, 0.1 and

Table 2
Formula of the La0.7Ca0.3
xBax(Mn13+− ΔMn 4Δ+ )Oy compounds as inferred from ICP analysis with the Δ and y stoichiometric coefficients related to Mn4 þ and O2
species as
deduced from iodometric titrations, density and compactness determined by helium pycnometry.

ICP results (accuracy of 0.02) Iodometric, Δ Titration, y Density Compactness (%)

x¼0 La0.69Ca0.31MnO3 0.232 2.966 4.88 7 0.02 83

x ¼ 0.1 La0.68Ca0.22Ba0.10MnO3 0.229 2.964 5.157 0.02 84
x ¼ 0.2 La0.69Ca0.12Ba0.19MnO3 0.231 2.965 5.477 0.02 85
218 F. Ayadi et al. / Journal of Magnetism and Magnetic Materials 381 (2015) 215–219

Fig. 6. Magnetization versus magnetic field of a representative sample, namely

x¼ 0.2, of the La0.7Ca0.3-xBaxMnO3 ceramic solid solution.

Fig. 5. Temperature dependence of magnetization at 50 mT of the whole

La0.7Ca0.3
xBaxMnO3 ceramic solid solution. below 0.5 T and tends to saturation for higher magnetic fields,
while it increases linearly in the whole explored magnetic field
0.2, respectively). When comparing these values to those inferred range at temperatures higher than TC.
from XRD (see crystallite size in Table 1 from 15 to 21 nm de- Using these data, the magnetic entropy change, ΔSM , was de-
pending on the sample), one can conclude that the grains are termined. Its variation versus temperature was obtained from the
polycrystalline. Moreover, they present facetted morphology sug- discreet form of the following relationship [30]:
gesting an efficient sintering even if a certain intergrain porosity Hmax ⎛ ∂M ⎞
subsists. The density of all the pellets (Table 2) corresponds to a ΔSM (T , H) = SM (T , H) − SM (T , 0) = ∫0 ⎜ ⎟ dH
⎝ ∂T ⎠H
compactness of about 85%, which is slightly lower than that
usually observed in solid state made manganites due to the low where Hmax is the maximum value of the external applied field.
sintering temperature. The magnetic entropy was plotted as a function of temperature
upon a magnetic field change of 5 T (see Fig. 7). As expected, it
3.2. Magnetic and magnetocaloric properties reaches its maximum at TC for each studied sample. The measured
max
ΔSM values were summarized in Table 3. They decrease slightly
Magnetization measurements versus temperature in the 10– from 2.62 to 2.33 J/(kg K) when the Ba content increases from x ¼0
350 K range were carried out under a magnetic field of 50 mT. The to 0.2, as previously observed by other authors on a quite
plotted M(T) curves confirmed the ferromagnetic behavior of the
equivalent system, the La0.7Ca0.3
xBaxMnO3 solid solution [29].
prepared samples. A net transition from the para- to the ferro- max
This ΔSM decrease is mainly attributed to the spin lattice in-
magnetic state can be clearly identified by decreasing the tem-
teraction decrease with the 〈rA〉 increase [31,32]. Using these va-
perature (Fig. 5). The Curie temperature (TC) values, inferred from
lues we also calculated the relative cooling power (RCP), applying
the minimum of the derivatives of M with respect to T, increases
the following expression [33]:
from 205 to 245 K when x increases from 0 to 0.2. This TC increase
is unambiguously related to the average ionic radius of A-site 〈rA〉 Max
RCP = − ΔSM (T , ΔH) δTFWHM
increase in the studied solid solution (Table 1). Indeed, the TC
variation in manganites is usually governed by the 〈rA〉 and/or the where δTFWHM is the full-width at half-maximum of ΔSM as a
charge carrier density changes [22,23]. In the present case, the function of temperature. RCP is important. It allows appreciating
substitution of divalent Ca2 þ by Ba2 þ does not affect the how the magnetocaloric effect may be extended over a large
Mn4 þ /Mn3 þ atomic ratio and then does not modify the carrier
density (see Table 2). It remains constant over the whole solid
solution composition range. Note that the oxygen deficiency in
these compounds remains also constant and only contributes in
weakening in the same way the double exchange interaction
strength in the whole solid solution. However, the divalent cation
substitution entails a decrease of the Mn–O bond length together
with an increase of the Mn–O–Mn angle (see Table 1). The main
consequence of such a structural feature is that the ferromagnetic
double exchange interaction between the Mn3 þ and Mn4 þ cations
is strengthened with the substitution ratio [24–26].
Compared to the TC values of conventionally made bulk mate-
rials (258, 284 and 320 K for x ¼0, 0.1 and 0.2 [27–29]) those
measured here are found lower (205, 225 and 245 K), in agree-
ment with the lower Mn4 þ concentration evidenced by iodometry
analysis.
The magnetization versus magnetic field up to 5 T was also
measured on the produced ceramics at different temperatures (see
Fig. 6). The plotted curves are typical of ferromagnets. At tem- Fig. 7. Magnetic entropy variation, ΔSM, as a function of temperature for a mag-
peratures lower than TC, the magnetization increases sharply netic field change of 5 T of the whole La0.7Ca0.3
xBaxMnO3 ceramic solid solution.
 F. Ayadi et al. / Journal of Magnetism and Magnetic Materials 381 (2015) 215–219 219

Table 3 important to take into account the SPS atmosphere which can lead
max
Curie temperature and maximum of the magnetic entropy variation ΔSM for a to oxygen non-stoichiometry.
magnetic field change of 5 T and Relative Cooling Power (RCP) of the
La0.7Ca0.3
xBaxMnO3 compounds.
Acknowledgments
Sample x ¼0 x ¼0.1 x¼ 0.2

TC (K) 205 225 245 The CMCU France-Tunisia Cooperation (CMCU N°13G1215) Re-
max
ΔSM (J/(kg K)) 2.62 2.51 2.33 search Program is thanked for financial support. The authors are
RCP (J/kg) 267.2 268.5 270.3 indebted to Dr. Y. Li (University Paris 6, France) for access to the
SQUID equipment.

Appendix A. Supplementary information

Supplementary data associated with this article can be found in

the online version at http://dx.doi.org/10.1016/j.jmmm.2014.12.047.

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