Journal of Magnetism and Magnetic Materials 401 (2016) 56–62

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Journal of Magnetism and Magnetic Materials

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

Effect of the annealing temperature on the structural and magnetic

behaviors of 0.875La0.6Ca0.4MnO3/0.125La0.6Sr0.4MnO3 composition
H. Gharsallah a,b, M. Bejar a,n, E. Dhahri a, E.K. Hlil c, M. Sajieddine d
a
Laboratoire de Physique Appliquée, Faculté des Sciences, Université de Sfax, B.P. 1171, 3000 Sfax, Tunisia
b
Institut Préparatoire aux Études d’Ingénieur de Sfax, Université de Sfax, BP 1172, 3018 Sfax, Tunisia
c
Institut Néel, CNRS Université J. Fourier, BP166, 38042 Grenoble, France
d
Laboratoire de Physique et Mécanique des Matériaux, Faculté des Sciences et Techniques, Université Sultan Moulay Slimane, BP 523, 23000 Béni-Mellal,
Morocco

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

Article history: The polycrystalline compounds of La0.6Ca0.4MnO3 (S0C1) and La0.6Sr0.4MnO3 (S1C0) were prepared using
Received 3 February 2015 the citric–gel method. With the resultant nanoparticle powders having crystallite size of 22.51 nm from
Received in revised form S0C1 and 27.39 nm from S1C0, the 0.875(S0C1)0.125(S1C0) composition was sintered at different tem-
6 September 2015
peratures: SC. 4-1 (at 700 °C), SC. 4-2 (at 900 °C), SC. 4-3 (at 1100 °C) and SC. 4-4 (at 1300 °C). XRD data
Accepted 25 September 2015
were analyzed by Rietveld refinement technique. The two S0C1 and S1C0 mother compounds were found
to crystallize in the rhombohedral and orthorhombic structure, respectively. The compounds sintered at
Keywords: 700 °C (SC. 4-1) and 900 °C (SC. 4-2) were found to present the two rhombohedral and orthorhombic
Perovskite phases corresponding to the mother compounds, which indicates that no interfacial reaction occurs.
Sintering temperature
However, when augmenting the sintering temperature, the formation of the 0.875(S0C1)0.125(S1C0)
Magnetic
new phase was observed. These observations were confirmed from the magnetization study, which
Orthorhombic distortion
revealed that the SC. 4-1 and SC. 4-2 compounds present two magnetic transitions temperature corre-
sponding to the two mother compounds. For higher sintering temperature (1100 and 1300 °C), we have
noted the presence of a new magnetic transition corresponding to the composition 0.875(S0C1)0.125
(S1C0) compound. The variation of the M(T) curves were discussed in terms of the orthorhombic dis-
tortion s2(Mn–O).
& 2015 Elsevier B.V. All rights reserved.

1. Introduction and the ionic size mismatch between the various A-site ion. The
Mn3 þ /Mn4 þ ratio is one of the parameters that can effectively
The manganite systems of the general formula RE1
xAExMnO3 control different interactions such as double exchange (DE) [12–
(RE¼ rare earth, AE¼Ca, Sr, Ba and Pb) offers a high degree of 15], super-exchange (SE) and Coulomb interaction among Mn ions.
chemical flexibility. Together with a complex interplay between Besides, it can modify the magneto-transport properties of man-
structure, electronic and magnetic properties, this leads to a very ganites. The average size of the A-site cations is another important
rich phase diagram involving various metallic, insulating and parameter that can influence the magnetic and electrical char-
magnetic phases [1–5]. Recently, the perovskite compounds have acteristics of these materials. It is well known that in the man-
been an intensive topic in scientific studies and potential tech- ganites exhibiting CMR, the ferromagnetic transition temperature
nological applications thanks to their charge and orbital ordering, (TC) increases with the increase in the average radius rA . In fact, a
magnetic phase transition, colossal magnetoresistance (CMR) ef- larger rA enhances the band width of the eg electron of Mn ion,
which favors DE interactions between Mn3 þ and Mn4 þ ions
fect as well as magnetocaloric effect (MCE) [6–8]. The strongly
through the bridging of oxygen ions. This stabilizes the FM me-
correlated structural, magnetic and transport properties have
tallic phase at low temperatures. At the same time, we should take
opened new areas of studying these materials from fundamental
into consideration the size difference between different cations
and application viewpoints [9–11]. These properties are sensitive
located in the A-site [16–18], which induces local distortions dis-
to the doping concentration x, which determines the Mn3 þ /Mn4 þ
tributed randomly in the sample volume and, consequently, causes
ratio to maintain the charge neutrality, the average cationic radii considerable variations of Mn–O–Mn bond lengths and angles [19–
23]. Tomioka and Tokura [24] have found that the A-site disorder
n
Corresponding author. Fax: þ216 74 676 609. has great effects on the properties of manganites and gives the
E-mail address: [email protected] (M. Bejar). phase diagram of disorder versus rA .

http://dx.doi.org/10.1016/j.jmmm.2015.09.082
0304-8853/& 2015 Elsevier B.V. All rights reserved.
 H. Gharsallah et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 56–62 57

Fig. 2. Observed (circle), calculated (continuous line) and difference patterns (at
the bottom) of X-ray diffraction data for La0.6Ca0.4 MnO3 (S0C1) and
La0.6Sr0.4 MnO3 (S1C0) compounds. The vertical tick indicates the allowed reflec-
Fig. 1. (a) Powder XRD patterns of La0.6 Ca0.4 MnO3 (S0C1) , La0.6Sr0.4 MnO3 (S1C0) tions. Asterisks show the presence of the minority secondary phase Mn3O4.
and 0.875 La0.6 Ca0.4 MnO3/0.125 La0.6Sr0.4 MnO3 compounds sintered at 700 °C (SC.
4-1), 900 °C (SC. 4-2), 1100 °C (SC. 4-3) and 1300 °C (SC. 4-4). (b) Zoom of the most
intense peaks: For the two compounds sintered at 700 °C (SC. 4-1) and 900 °C (SC.
4-2), we deduced that they were well represented by a simple combination of S0C1 range of temperatures, ranging from E 260 to E 370 K in the first
and S1C0 compounds, indicating that no interfacial reaction occurred. By increasing case. In the second case, a narrower peak of the MCE is expected at
the sintering temperature to 1100 °C, the width of the main peak decreased and room temperature.
underwent a displacement towards low angles, which means not only that the
contribution of the peaks characteristic of S1C0 and S0C1 compounds drop sig-
nificantly, but also that a new phase is formed.
2. Experiment

La0.6Ca0.4MnO3 and La0.6Sr0.4MnO3 compounds are one of the 2.1. Sample preparation
two most intensively studied series of manganites [25–29], due to
their strong coupling between magnetic structure and crystal The polycrystalline samples of La0.6Ca0.4MnO3 (S0C1) and
lattice distortions. These two compounds, having a similar La0.6Sr0.4MnO3 (S1C0) were prepared by the citric–gel method
Mn3 +/Mn4 + ratio but different average ionic radii of the A-site, [30–32] using La (NO3 )3 6H2 O, Ca (NO3 )2 4H2 O, Mn (NO3 )2 6H2 O and
present a ferromagnetic order below the critical temperature TC Sr (NO3 )2. These precursors were dissolved in deionized water in a
(E 260 K for La0.6Ca0.4MnO3 and E370 K for La0.6Sr0.4MnO3). separate beaker and mixed with the solution of citric acid and
The aim of this research work is to study the effect of the ethylene glycol, at constant stirring, in the ratio of (1
tuning sintering temperatures on the structural and magnetic [ Mn (NO3 )2 6H2 O])/(1[citric acid]/ 2 [ethylene]) to get a transparent
3
behaviors of La0.6Ca0.4MnO3/La0.6Sr0.4MnO3 composition prepared stable solution. The obtained solution was then heated at 80 °C to
via citric–gel method. eliminate excess water and the resulting solution was converted
It is estimated that while the mixture sintered at low tem- into viscous glassy gels and dried at 120 °C to get dark grayish
peratures will present two separate phases, the one sintered at flakes. In order to ensure that the decomposition of nitrate/citrate
high temperatures will be single phase. complexes, the organic components and the residual organic
Therefore it is expected that: compounds of the precursor, the flakes were ground, calcined at
700 °C for 12 h and converted into pellets [33,34]. These pellets
1. An overlapping peaks, giving the variation of the magnetic en- were further annealed at 900 °C for 18 h to get the desired man-
tropy change in the composite obtained at low temperatures. ganites nanoparticles.
2. A merger of peaks, showing the variation of the magnetic en- The (0.875(S0C1))(0.125(S1C0)) composition was obtained by a
tropy change of the two mother compounds for the mixture stoichiometric proportion of the (S0C1) and (S1C0) powders. By
sintered at high temperatures. sintering the composition, at various temperatures of 700 (SC-4.1),
900 (SC-4.2), 1100 (SC-4.3) and 1300 °C (SC-4.4) for 24 h in air, four
Under these conditions, an MCE will be obtained over a wide samples were prepared.
58 H. Gharsallah et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 56–62

Table 1
Refined structural parameters for La0.6 Ca0.4 MnO3 (S0C1) and La0.6Sr0.4 MnO3
(S1C0) compounds.

Compound S0C1 S1C0

Space group R 3̄c 100.00 (3.05) P bnm 100.00 (1.72)

a=b≠c a≠b≠c
α = β = 90° et γ = 120° α = β = γ = 90°
a (Å) 5.44215 (0.00077) 5.50255 (0.00041)
b (Å) 5.44215 (0.00077) 5.45739 (0.00038)
c (Å) 13.32140 (0.00386) 7.72742 (0.00063)
Mult = 6 Mult = 4
La, Ca, Sr sites 0.00000 (0) 0.99775 (0)
(x,y,z) 0.00000 (0) 0.01887 (0)
0.75000 (0) 0.25000 (0)
Mult = 6 Mult = 4
Mn site 0.00000 (0) 0.50000 (0)
(x, y, z) 0.00000 (0) 0.00000 (0)
0.00000 (0) 0.00000 (0)
Mult = 18 Mult = 4
O1 0.44369 (0) 0.07574 (0)
(x, y, z) 0.00000 (0) 0.51352 (0)
0.25000 (0) 0.25000 (0)
Mult = 8
O2 0.71142 (0)
(x, y, z) 0.28905 (0)
0.01563 (0)
V(Å3) 56.947 (0.020) 58.01275 (0.0075)
Mn- O1-Mn (°) 161.89705 (5) 155.28496 (15)
Mn- O2-Mn (°) 161.00447 (13)
dMn- O1 (Å) 1.94790 (10) 1.97767 (8)
dMn- O2 (Å) 1.96376 (12)
1.96505 (12)
o dMn − O 4(Å) 1.96883 (10)
σ 2 < Mn − O 4 6.5546  10
5
RF (%) 0.720 3.90 Fig. 4. Observed (circle), calculated (continuous line) and difference patterns (at
RB (%) 0.771 2.69 the bottom) of X-ray diffraction data for SC. 4-1 and SC. 4-2 compounds. The ver-
Rp (%) 14.3 13.5 tical tick indicates the allowed reflections. Asterisks show the presence of the
Rwp (%) 9.62 9.95 minority secondary phase Mn3O4.
Rexp (%) 7.58 6.12
Chi2 (%) 1.61 2.64
o rA 4(Å) 1.2016 1.2536
2.3. Transmission electron microscopy (TEM)

The morphologies of the surfaces and fracture surfaces of all

0.5 samples were observed by Transmission Electron Microscopy
I (SC4-1)
Normalized diffracted intensity

I (SC4-2) (TEM). Surfaces were covered with carbon before microscopic

0. 875 I (S0C1) + 0.125 I (S1C0) observation.
0.4

2.4. Magnetic measurements

0.3

Magnetic measurements were performed in BS1, BS2 and squid

0.2 magnetometer developed in Louis Neel Laboratory of Grenoble.
The magnetization curves were obtained under an applied mag-
0.1
netic field of 0.05 T and with a temperature ranging from 5 to
500 K.

0.0
40 44 48 52 56 60
2 θ (°) 3. Results and discussion
Fig. 3. Comparison between the diffraction intensities of SC. 4-1 and SC. 4-2
compounds and the calculated one for 0.875 S1C0 þ0.125 S0C1 compound. 3.1. Characterization structural and crystallite size

The X-ray diffraction patterns of our synthesized samples are

2.2. X-ray diffraction reported in Fig. 1a with a zoom of the most intense peaks (Fig. 1b).
For all samples, the presence of a secondary phase attributed to
The crystalline structure and phase purity of the prepared the unreacted Mn3O4 was noted. The phase identification, based
samples were examined by powder X-ray diffraction with CuKα on X-ray diffraction results, is shown in Fig. 2. The Rietveld re-
radiation (λ = 1.5406 Å), at room temperature, by a step scanning finements of the XRD data performed using Fullprof program re-
vealed that the two mother samples, S0C1 and S1C0, are indexed
of 0.016° in the range of 20° ≤ 2θ ≤ 90°. The data were analyzed by
in the rhombohedral structure with R-3c space group and or-
the Rietveld method using the Fullproof SOFTWARE [35].
thorhombic system with Pbnm space group, respectively. The
unindexed peaks corresponding to the Mn3O4 minor secondary
 H. Gharsallah et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 56–62 59

Table 2
Refined structural parameters at room temperature of ((S0C1)0.875 (S1C0)0.125 )
compounds sintered at 700 °C (SC. 4-1) and 900 °C (SC. 4-2).

Compound SC. 4-1 (sintered at 700 °C) SC. 4-2 (sintered at 900 °C)

Space group Phase 1: Phase 2: Phase 1: Phase 2:

¯
R 3c P bnm ¯
R 3c P bnm
S0C1 SC01 S0C1 SC01
Fract (%): 87.48 (0.61) 12.52 (0.06) 86.80 (0.03) 13.20 (0.03)
a (Å) 5.45617 5.31137 5.46227 5.10143
(0.00087) (0.00521) (0.00029) (0.00727)
b (Å) 5.45617 5.51077 5.46227 5.71925
(0.00087) (0.00575) (0.00029) (0.00801)
c (Å) 13.35072 7.98005 13.33203 7.95088
(0.00383) (0.00210) (0.00105) (0.01073)
La, Ca, Sr site 0.00000 (0) 0.99775 (0) 0.00000 (0) 0.99775 (0)
(x, y, z) 0.00000 (0) 0.01887 (0) 0.00000 (0) 0.01887 (0)
0.75000 (0) 0.25000 (0) 0.75000 (0) 0.25000 (0)
Mn site (x, y, z) 0.00000 (0) 0.50000 (0) 0.00000 (0) 0.50000 (0)
0.00000 (0) 0.00000 (0) 0.00000 (0) 0.00000 (0)
0.00000 (0) 0.00000 (0) 0.00000 (0) 0.00000 (0)
O1 (x, y, z) 0.44321 (0) 0.07574 (0) 0.44321 (0) 0.07574 (0)
0.00000 (0) 0.51352 (0) 0.00000 (0) 0.51352 (0)
0.25000 (0) 0.25000 (0) 0.25000 (0) 0.25000 (0)
O2 (x, y, z) 0.71142 (0) 0.71142 (0)
0.28905 0.28905
(0) 0.01563 (0) (0) 0.01563 (0)
V (Å3) 344.201 233.574 (0.340) 344.487 231.977
(0.126) (0.038) (0.559)
V/FU (Å3) 57.366 58.393 (0.085) 57.414 57.994 (0.139)
(0.021) (0.06)
Mn- O1-Mn (°) 161.74 (4) 156.82 (6) 161.728 (11) 157.6 (3)
Mn- O2-Mn (°) 160.89 (17) 161.0 (2)
dMn- O1 (Å) 1.9531 (3) 2.0365 (5) 1.95370 (8) 2.026 (3)
dMn- O2 (Å) 1.9529 (15) 1.978 (2)
1.9277 (14) 1.9073 (19)
o dMn − O 4 1.9531 (3) 1.9723 (11) 1.95370 (8) 1.97043 (8) Fig. 5. Observed (circle), calculated (continuous line) and difference patterns (at
(Å) the bottom) of X-ray diffraction data for SC. 4-3 and SC. 4-4 compounds. The ver-

3
2
σ 2 < Mn − O 4 2.42  10 0 2.39  10 tical tick indicates the allowed reflections. Asterisks show the presence of the
RF (%) 2.00 15.7 1.10 14.3 minority secondary phase Mn3O4.
Rb (%) 2.80 14.1 1.91 24.3
Rp (%) 17.5 14.5
Rwp (%) 11.4 10.5
Rexp (%) 8.25 6.76
low angles (Fig. 1b), which means not only that the contribution of
Chi2 (%) 1.90 2.42 the peaks characteristic of S1C0 and S0C1 compounds drop sig-
nificantly, but also that a new phase is formed.
The Rietveld refinement of the XRD patterns of SC. 4-3 com-
phase (I41/amd) are marked by asterisk (*) [36,37]. The related pound (Fig. 5), sintered at 1100 °C, shows that the main phase
refined structural parameters of S0C1 and S1C0 compounds are La0.6Ca0.35Sr0.05MnO3, with a percentage of about 99% (Table 3), is
given in Table 1. We note that the unit cell volume per formula indexed in the orthorhombic system with Pbnm space group. We
unit (V/Z) increases from 56.947 Å3 for S0C1 to 58.01275 Å3 for also note the presence, with a percentage of about 1%, of the two
S1C0. This increase can be due to the fact that the cationic radius mother compounds (S0C1 and SC01), which indicates that this
of the strontium ion (r (Sr2 +) = 1.31 Å) is higher than that of the temperature is not sufficient to obtain a complete reaction be-
calcium one (r (Ca2 +) = 1.18 Å) [38], which causes an enhancement tween S0C1 and SC01 compounds. However, upon increasing the
of the average A-site radius rA from 1.2016 Å for S0C1 to 1.2536 Å sintering temperature up to 1300 °C, the interfacial reaction be-
for S1C0, as given in Table 1. came complete and led to the formation of the pure phase of
After the formation of the two mother compounds, S1C0 and La0.6Ca0.35Sr0.05MnO3 (Fig. 5 and Table 3). The crystallite size of the
S0C1, had been confirmed, we prepared the compound with compounds can be estimated by using the SCHERRER formula
composition (0.875 (S0C1)) (0.125(S1C0)). For the two first com- [39]:
pounds sintered at 700 °C (SC. 4-1) and 900 °C (SC. 4-2), we de-
0.9 × λ
duced that they were well represented by a simple combination of D=
S0C1 and S1C0 compounds, indicating that no interfacial reaction β × cos (θ )
occurred. This deduction was confirmed by the fact that the DRX where λ is the used wavelength (λ ¼1.540560 Å), 2θ is the position
intensities of the SC. 4-1 and SC. 4-2 compounds are equal to the of the most intense peak and β is the full width at half maximum
sum of those of the S1C0 and S0C1 compounds, respectively, (FWHM) of the same peak. From Table 4, it can be noted that all
multiplied by 0.875 and 0.125 proportions (Fig. 3). These ob- samples present a nanometric crystallite size, which is found to be
servations were also verified using the Rietveld refinements equal to 22.51, 27.39 and 28.30 nm for SOC1, S1CO and SC. 4-4
(Fig. 4) of the XRD patterns, which reveal the presence of the compounds, respectively.
rhombohedral and orthorhombic structures with proportions
close to those desired. The results of the Rietveld refinements for 3.2. Transmission electron microscopy (TEM)
these compounds are summarized in Table 2.
By increasing the sintering temperature to 1100 °C, the width of Fig. 6a, b and c show examples of the top view of the surface
the main peak decreased and underwent a displacement towards morphologies of S0C1, S1C0 and SC. 4-4 compounds, respectively.
60 H. Gharsallah et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 56–62

Table 3
Refined structural parameters of SC 4-3 and SC. 4-4 compounds sintered at 1100 and 1300 °C, respectively.

Compound SC. 4-3 (sintered at 1100 °C) SC. 4-4 (sintered at 1300 °C)

Space group Phase 1: Pbnm Phase 2: Pbnm Phase 3: R3̄c Pbnm

La0.6 Ca0.35 Sr0.05 MnO3 La0.6Sr0.4 MnO3 La0.6 Ca0.4 MnO3 La0.6 Ca0.35 Sr0.05 MnO3
Fraction (%): 99.08 (0.55) 0.45 (0.54) 0.47 (0.12) 100.00 (2.97)
a (Å) 5.46903 (0.00056) 5.50255 (0.00000) 5.44214 (0.00000) 5.46886 (0.00064)
b (Å) 5.45099 (0.00033) 5.45738 (0.00000) 5.44214 (0.00000) 5.44855 (0.00059)
c (Å) 7.69725 (0.00042) 7.72741 (0.00000) 13.32136 (0.00000) 7.69322 (0.00079)
La, Ca, Sr site (x, y, z) 0.99750 (107) 0.99775 (0) 0.00000 (0) 0.99871 (236)
0.01421 (41) 0.01887 (0) 0.00000 (0) 0.00960 (98)
0.25000 (0) 0.25000 (0) 0.75000 (0) 0.25000 (0)
Mn site (x, y, z) 0.50000 (0) 0.50000 (0) 0.00000 (0) 0.50000 (0)
0.00000 (0) 0.00000 (0) 0.00000 (0) 0.00000 (0)
0.00000 (0) 0.00000 (0) 0.00000 (0) 0.00000 (0)
O1site (x, y, z) 0.04366 (291) 0.07574 (0) 0.44369 (0) 0.05005 (510)
0.48251 (271) 0.51352 (0) 0.00000 (0) 0.49104 (717)
0.25000 (0) 0.25000 (0) 0.25000 (0) 0.25000 (0)
O2site (x, y, z) 0.71108 (234) 0.71142 (0) 0.70504 (418)
0.28083 (309) 0.28905 (0) 0.28774 (483)
0.03809 (121) 0.01563 (0) 0.03729 (204)
V (Å3) 229.468(0.030) 232.051 (0.000) 341.679 (0.000) 229.238 (0.043)
V/FU (Å3) 57.367(0.007) 58.012 (0.000) 56,9465 (0.000) 57.309 (0.010)
Mn- O1-Mn (°) 162.33(05) 155.28496 161.89705 162.33(11)
Mn- O2-Mn (°) 158.89(2) 161.00447 158.90(7)
dMn- O1 (Å) 1.947(5) 1.97767 1.94790 1.948(3)
dMn- O2 (Å) 1.937(12) 1.96376 1.937(16)
1.991(12) 1.96505 1.991(16)
dMn − O (Å) 1.958(10) 1.96882 1.94790 1.964(3)
σ 2Mn − O 1.856  10
3 6.563  10
5 0 1.687  10
3
Rf (%) 1.79 3.55 1.17 5.18
Rb (%) 1.23 3.59 1.33 2.55
Rp (%) 11.9 23.9
Rwp (%) 8.06 13.5
Rexp (%) 6.56 9.77
Chi2 (%) 1.51 1.90

Table 4 variance of the A-cation radius distribution noted s2, formed by

Data relating to the most intense peak: position, Full Width at half maximum, both the variance in the distribution of Mn–O and A–O distances
observed intensity, calculated intensity, relative uncertainty committed in the in- s2(Mn–O) and s2(A–O), respectively [41]. The s2(Mn–O) quantifies
tensities and crystallite size.
the orthorhombic distortion and s2(A–O) quantifies the local one.
Sample 2θ (°) FWHM (β ) (°) Iobs (a.u.) Ical (a.u.) ΔI D (nm) An orthorhombic distortion induces the localization of the carriers,
(% )
I and therefore leads to the reduction of the ferromagnetic behavior
S0C1 32.889 0.36804 3406 3404 0.06 22.51
and increase of the super-exchange antiferromagnetic interac-
S1C0 32.704 0.30232 4752 4745 0.14 27.39 tions. This may explain the difference between the magnetization
SC 4-4 32.844 0.29262 2259 2258 0.00 28.30 values of S0C1 and S1C0 compounds. In fact, for S1C0 compound,
crystallized in the orthorhombic structure, the contribution of
both orthorhombic and local distortions is evident, inducing a
The estimated average grain sizes are about 117, 96 and 55 nm for clear decrease of the ferromagnetic interactions, and thus a re-
S0C1, S1C0 and SC.4-4, respectively. These values are slightly duction of the magnetization. However, for the S0C1 compound,
higher than those of the crystallite sizes determined previously the structural transition to the rhombohedral phase is character-
from the Scherer formula related to X-ray diffraction patterns. ized by a suppression of the orthorhombic distortion s2(Mn–O),
but the local distortion s2(A–O) continues to exist. The suppres-
3.3. Magnetic properties sion of the orthorhombic distortion is accompanied by a deloca-
lization of carriers between the Mn ions, leading to an enhance-
The magnetization and its derivative vs. temperature curves for ment of the ferromagnetic behavior, which can explain the clear
all compounds were measured under an applied magnetic field of increase of the magnetization for S0C1 compound.
0.05 T (Fig. 7a). The mother compounds S0C1 and S1C0 present a At this level, the effect of the sintering temperature on the M
magnetic transition from a paramagnetic to a ferromagnetic state (T) curves behavior will be discussed. Indeed, for the SC. 4-1 and
at the Curie temperature TC , defined as the minimum of the first SC. 4-2 compounds sintered at 700 and 900 °C, respectively, the M
derivative of the magnetization (Fig. 7b). The TC values were found (T) curves present a similar behavior with the existence of two
to increase from 255 to 355 K for S0C1 and S1C0, respectively. magnetic transitions. Actually, as previously mentioned in the
These values are in agreement with those determined by Nasri structural study, these two compounds present the main rhom-
et al. [40] for the same compounds prepared by the traditional bohedral phase, with a percentage of about 87% for both com-
solid state reaction method. pounds, and a secondary orthorhombic structure with a little
From the M(T) curves, it is worthy to note that the magneti- percentage (∼13%). As it is well-known for the two sintering
zation (M) value for the S0C1 compound is higher than the S1C0 temperatures of 700 and 900 °C, there is no reaction between
one. This apparent difference can be due to the effect of the S0C1 and S1C0 compounds. So, the main rhombohedral phase is
 H. Gharsallah et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 56–62 61

S0C1
SC 4-1
1.2 SC 4-2
SC4-3

Magnetization ( µB/Mn)
SC4-4
S1C0
0.9

0.6

0.3

0.0
0 100 200 300 400 500
Temperature (K)

dM/dT ( µB .K /Mn)
-1
S0C1
SC 4-1
SC 4-2
SC 4-3
SC 4-4
S1C0

0 100 200 300 400 500

Temperature (K)

Fig. 7. The temperature dependence of the (a) magnetization and (b) temperature
dM
derivative .
dT

structure becomes dominant, which explains the diminution of

the magnetization value in comparison with the S0C1 one. On the
other hand, we come to the conclusion that the presence of the
little percentage of the rhombohedral S0C1 structure induces a
clear difference in the magnetization value compared to the S1C0
one presenting only the orthorhombic phase. For the sintering
temperature of 1300 °C, what is worthy to note is the presence of
the pure orthorhombic La0.6Ca0.35Sr0.05MnO3 phase, ferromagnetic
Fig. 6. TEM micrograph of particle size of (a) La06Ca0.4MnO3 (S0C1), (b)
below the Curie temperature 290 K, characterized by the lower
La06Sr0.4MnO3 (S1C0) and (c) La06Ca0.35Sr0.05MnO3 (SC. 4-4).
magnetization value due to the double effect of the orthorhombic
distortion s2(Mn–O).
related to the SOC1 compound and the orthorhombic one is cor- Finally, the magnetization value of SC. 4-4 compound, pre-
related to the S1CO compound. As the rhombohedral structure is senting a pure orthorhombic structure, is lower than that of S1C0
dominant for both SC. 4-1 and SC. 4-2 compounds, a similitude of one, also presenting an orthorhombic phase. This difference can be
the magnetization behaviors and values at low temperature with related to the fact that the orthorhombic distortion s2(Mn–O) is
the SOC1 one can be noted. However, when increasing the tem- more pronounced for the SC. 4-4 compound (see Tables 1 and 3),
perature, a little difference between the M(T) curves of S0C1 which may lead to more robust antiferromagnetic interactions.
compound and those of SC. 4-1 and SC. 4.2 ones can be seen. This
difference can be related to the secondary orthorhombic phase,
confirming the existence of the orthorhombic S1C0 structure. The 4. Conclusion
presence of the two S0C1 and S1C0 structures is confirmed from
the dM/dT(T) curves (Fig. 7b), which reveals the presence of two The effect of the sintering temperature on the structural and
peaks, and as results the two magnetic transitions at about 260 magnetic properties of 0.875(S0C1)0.125(S0C1) compositions
and 360 K, related to S1C0 and S0C1 compounds, respectively. prepared via the citric–gel method has been investigated. The
Continuing to augment the sintering temperature, a dramatic nanometric size of the obtained powders was demonstrated on
change of the M(T) curves for SC. 4-3 and SC. 4-4 compounds can the basis of the X-ray diffraction and confirmed by TEM images.
be clearly observed. This change can be explained by the in- The magnetic study has revealed that compounds sintered at 700
troduction of a new structure that is different from that of all other and 900 °C present two magnetic transitions, corresponding to the
compounds. In fact, for SC. 4-3 compound, the structural study has two S0C1 and S1CO mother compounds. The magnetization tem-
revealed the presence of a main orthorhombic structure related to peratures values, determined at low temperatures, were found to
the formation of a new La0.6Ca0.35Sr0.05MnO3 compound with a be close to the S0C1 compound, which indicates the dominance of
little percentage of the two S0C1 and S1C0 mother compounds. So, the S0C1 rhombohedral phase. When increasing the sintering
for SC. 4-3 compound the contribution of the orthorhombic temperature, the M(T) curves showed the introduction of a new
62 H. Gharsallah et al. / Journal of Magnetism and Magnetic Materials 401 (2016) 56–62

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