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Physica B 519 (2017) 69–75

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Physica B
journal homepage: www.elsevier.com/locate/physb

Observation of magnetization reversal and magnetocaloric effect in MARK


manganese modified EuCrO3 orthochromites

Surendra Kumara, Indrani Coondoob, M. Vasundharac, Venkata S. Pulid, Neeraj Panwara,
a
Department of Physics, Central University of Rajasthan Bandarsindri, 305817 Ajmer, Rajasthan, India
b
Department of Physics & CICECO-Aveiro Institute of Materials, University of Aveiro, 39810-193 Aveiro, Portugal
c
Materials Science and Technology Division, CSIR-National Institute for Interdisciplinary Science and Technology, Industrial Estate, Trivandrum 695019,
India
d
Department of Physics and Engineering Physics, Tulane University, New Orleans, LA 70118, USA

A R T I C L E I N F O A BS T RAC T

Keywords: We report here an investigation on the structural, magnetic and magnetocaloric properties of Mn doped
1. Chromites EuCr0.85Mn0.15O3 (ECMO) chromites synthesized via ceramic route. The compound crystallized into distorted
2. Magnetization reversal orthorhombic structure with Pnma space group similar to that of its parent EuCrO3 compound, as revealed from
3. Spin reorientation the refined of x-ray powder diffraction pattern, but with an increase in the lattice volume. Neel temperature,
4. Magneto- caloric effect
noticed at 162 K from the temperature variation of magnetization, smaller than that reported for pristine
EuCrO3; indicated the influence of Mn3+ substitution in decreasing the antiferromagnetic ordering.
Magnetization reversal evolved in the studied compound under lower field while such feature was absent in
the undoped EuCrO3. Magnetocaloric effect was measured through the magnetic entropy change and relative
cooling power. Near the spin reorientation transition temperature ~ 40 K, the magnetic entropy change was
equal to 3.788 J kg−1 K−1 under 90 kOe field with 215.22 J kg−1relative cooling power. The results have been
understood in terms of the competition between Cr-rich clusters, Mn-rich clusters and local Mn-Cr ordered
clusters and their different temperature dependency.

1. Introduction of their rotation [17,18]. This causes slight canting of Cr3+ions, which
should otherwise be antiparallel to each other; resulting in a weak
Rare-earth orthochromites with the general formula RCrO3 (R = Y ferromagnetic (WFM) behaviour below TN. The Cr3+ ions produce an
or trivalent rare-earth ion) have seen an unprecedented surge of internal field at the rare-earth site, which is opposite to the magnetiza-
worldwide research due to their peculiar magnetic properties. For tion of WFM component of Cr3+ ions. The magnetic moment of the
example, below the Neel temperature (TN); they exhibit canted anti- rare-earth ion (if it is magnetic) gets aligned by the internal field
ferromagnetic (CAFM) behaviour, temperature induced magnetization opposite to that of Cr3+ ions. Above a particular temperature known as
reversal (TIMR), exchange bias (EB) and spin reorientation (SR) [1–6]. compensation or crossover temperature, magnetization of Cr3+ ions
Their TN's lie in the range between orthomanganites and orthoferrites. dominates the rare-earth ion's magnetic moment and thereby resultant
The orthochromites have also demonstrated ferroelectric polarization magnetization is positive. However, as the temperature lowers and
either induced by an external magnetic field (ME) or a spontaneous passes the compensation temperature, the latter overcomes the former,
polarization as a consequence of internal magnetic fields induced by resulting in negative magnetization or magnetization reversal (MR)
long-range magnetic ordering (thus exhibiting the multiferroic beha- [1,2,4,16]. Such interesting behaviour of MR is also reported upon
viour) [7–12]. These properties make them suitable for spintronics, partial replacement of Cr ions with the transition metal elements such
sensors, thermally assisted random access memory devices etc. [13– as Mn and Fe [19–22]. Recently, a prominent MR behaviour is
16]. The orthochromites generally crystallize into distorted orthorhom- reported in 15% of Mn- substituted La-chromites [19] and Sm-
bic crystal structure with Pnma space group. The distortion from the chromites [20]. In addition to chromites, the MR effect has also been
ideal cubic perovskite structure is mainly in the dodecahedral rare- reported in several other systems like vanadates [23,24] and manga-
earth sites, resulting in the geometrical structure factor, t < 1. The nites [25,26]. In orthovanadates, the MR arises from the effects of
Cr3+ ions occupy the octahedral sites, which are less distorted by virtue antisymmetric Dzyloshinsky-Moriya (DM) interaction and magnetos-


Corresponding author.
E-mail addresses: neerajpanwar@curaj.ac.in, neeraj.panwar@gmail.com (N. Panwar).

http://dx.doi.org/10.1016/j.physb.2017.05.050
Received 1 May 2017; Received in revised form 21 May 2017; Accepted 26 May 2017
Available online 27 May 2017
0921-4526/ © 2017 Elsevier B.V. All rights reserved.
S. Kumar et al. Physica B 519 (2017) 69–75

Fig. 1. (a) XRD pattern and (b) the crystal structure of ECMO ceramic.

trictive distortion induced by orbital moments [27,28]. Recently, which were finally sintered at 1350 °C for 24 h in air. The phase
another interesting phenomenon called magnetocaloric effect (MCE) identification was carried out by x-ray diffractometer (PANalytical-
has aroused interest in chromites [20,21,29,30]. MCE is a working Empyrean) using Cu Kα radiation with wavelength 1.5404 Å at a
principle of magnetic refrigeration, which is a potential technology to scanning rate of 0.01° per second from 20° ≤ θ ≤ 80°. Temperature and
compete with conventional vapour-compression based refrigerants that field variations of magnetization measurements were carried out using
besides being expansive are detrimental to environment also. vibrating sample magnetometer attached to a physical property
Chromites exhibit enhanced MCE in the spin reorientation region at measurement system (PPMS) (Quantum Design Inc., USA).
low temperatures [20,21,29,30]. Magnetization versus temperature (M-T) curves were obtained in the
The europium orthochromite EuCrO3 is a known orthorhombic G- temperature range 2–300 K in both zero field cooled (ZFC) and field
type antiferromagnetic (AFM) insulator with TN around 181 K [31– cooled (FC) modes under different applied magnetic field. Here, zero
33]. Taheri et al. investigated the magnetic properties of nano-sized field cooled defines the protocol by cooling the sample from room
EuCrO3 powders, synthesized by a solution combustion method, using temperature to 2 K in zero external magnetic field and then collecting
DC/AC magnetization measurements [31]. An exchange bias effect, magnetization data in warming cycle under applied magnetic field.
magnetization irreversibility and AC susceptibility dispersion in nano- Whereas, field cooled measurements were performed by cooling the
particles provided evidence for the presence of the spin disorder sample under the applied magnetic field to 2 K and then measuring the
magnetic phase. In another study, Taheri et al. observed an anomaly magnetization during heating. Magnetization versus magnetic field (M-
near 100 K in magnetization, lattice parameters, thermal expansion, H) data was acquired at different temperatures between 2 and 180 K in
Raman spectroscopic, permittivity, and conductance measurements of zero field cooled mode.
EuCrO3 nanopowders. This anomaly was attributed to the magnetoe-
lastic distortion in the EuCrO3 crystal [34]. Deng et al. detected phase
separation and exchange bias effect in Ca doped EuCrO3 ceramics [35]. 3. Results and discussion
From this, one can notice that fewer studies, however, have been
reported on the partial substitution of the Cr3+ ion in EuCrO3 by other 3.1. Structural characterization
cations. For example, Widatallah et al. have studied the structural,
magnetic and Mossbauer studies of mechanosynthesized nanocrystal- Fig. 1a illustrates the powder XRD pattern and the Rietveld
line EuCr1−xFexO3 particles [36]. They found that with increasing Fe3+ refinement (using FullProf program) results of the crystal structure
ion concentration the average crystallite size decreases, the lattice of polycrystalline ECMO sample. It can be noticed that all the peaks are
parameters increase and the distortion of the orthorhombic unit cell indexed by an orthorhombic G-type (a > b /√2 > c ) structure with
gets more pronounced. Magnetic measurements have shown the Pnma space group. The lattice volume of the ECMO compound is
particles to be essentially antiferromagnetic with a slight spin canting, greater than reported for the corresponding undoped bulk ceramic and
resulting in weak ferromagnetism. Keeping in mind all the above single crystal of EuCrO3 sample in literature [36–38]. This can be
issues, we have chosen 15% Mn3+ ions substituted Eu-chromite. attributed to the fact that Mn3+(0.645 Å) ion has larger ionic radius as
Hence, in the present work, we have investigated the effect of partial compared to that of Cr3+ion (0.615 Å) and absence of secondary phases
substitution of Mn at the Cr sites on the structural, magnetic and in the XRD pattern confirms Mn3+ substitution at the Cr3+sites [39].
magnetocaloric properties of polycrystalline EuCr0.85Mn0.15O3 ortho- The lattice volume of the present compound is the least among other
chromite compound. To the best of our knowledge such studies 15% Mn-doped LaCrO3 (LCMO) and SmCrO3 (SCMO) compounds
especially the magnetocaloric properties have not been performed on which is reasonable to believe as Eu3+ (1.066 Å) ionic size is smaller
doped EuCrO3 compound and we report it in this article for the first than La3+ (1.16 Å) and Sm3+ (1.079 Å) ions [19,20]. The complete
time. crystal structure details and refined parameters are presented in
Table 1. In ECMO, the Cr3+/Mn3+ions are octahedrally coordinated
by oxygen ions and Eu3+ ions are located at the interstitial space among
2. Experimental details the (Cr/Mn)O6 octahedra (see crystal structure of Fig. 1b made using
VESTA software [40]). The octahedral titling should have an influence
Polycrystalline samples of EuCr0.85Mn0.15O3 (ECMO) were pre- on the (Cr/Mn)–O bond lengths and (Cr/Mn)–O–(Cr/Mn) bond
pared through solid state reaction method by taking high purity Eu2O3 angles, which for the present sample are listed in Table 1. Further,
(99.9%), MnO2 (99.99%) and Cr2O3 (99.9%) as starting materials (all the Eu–O and B–O (where B: Cr/Mn) bond lengths were used for the
from Sigma Aldrich, U.S.A.). The mixtures were thoroughly ground and calculation of Goldschmidt tolerance factor t ≡ (Eu − O)/ 2 ×(B − O)
first calcined for 24 h at 600 °C followed by crushing and second and a value of t < 1 results in significant cooperative rotations of the
calcination at 900 °C for 12 h. After second calcination, the powder was BO6 octahedra. The orthorhombic distortion of the unit cell from the
pulverized and pelletized in the form of uniform and compact pellets, ideal cubic structure, defined by the orthorhombic strain factor

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S. Kumar et al. Physica B 519 (2017) 69–75

Table 1 rich clusters, Mn-rich clusters and local Mn–Cr ordered clusters. The
List of structural parameters from the Rietveld refinement with a reliability factors of RF spin structure of the Cr-rich regions is of Γ4-type with the net canted
= 2.68%, RBragg = 3.37% and goodness of fitting ( χ2) = 3.08.
moment along the c axis, while the Mn-rich and Mn–Cr ordered
Lattice parameters regions is of Γ2-type with the net moment along a and c axis,
a (Å) b (Å) c (Å) volume(Å3) density (g / respectively. According to Kanamori-Goodenough (KG) rules [42],
cm3) the Cr3+–O2-–Cr3+ and Mn3+–O2-–Mn3+ interactions are AFM while
5.5331(3) 7.6133(4) 5.3425(3) 225.06 7.431 the Mn3+–O2-–Cr3+ interaction is FM or ferrimagnetic (FIM). Further,
Atomic positions
the Cr-rich regions and the Mn-Cr ordered regions are coupled
Wyckoff x y z Occ. antiferromagnetically. As a result, the net moments of the two regions
positions orient in the opposite direction and they may have different tempera-
Eu 4c 0.0573(4) 1/4 −0.0126(7) 0.95523 ture dependency. At temperatures just between Tcomp and TN i.e. Tcomp
Cr 4b 0 0 1/2 0.85058
< T < TN, the net magnetization of Cr-rich regions aligned along the
Mn 4b 0 0 1/2 0.14979
O1 4c 0.482(4) 1/4 0.108(3) 0.99672 applied field is larger than that of the Mn-Cr ordered regions aligned
O2 8d 0.295(4) 0.056 −0.287(4) 1.93285 opposite to the applied field. When the temperature decreases below
(2) Tcomp, net magnetization of the latter becomes larger than that of the
former one, leading to the occurrence of temperature induced magne-
Bond distance and bond angles
Mn/Cr–O1 Eu–O1 (Å) Mn/Cr–O1–Mn/Cr Mn/Cr–O2–Mn/Cr (deg.)
tization reversal [22]. At temperatures below Tcomp, when the applied
(Å) (deg) field is large enough, Mn-Cr ordered clusters would tend to be rotated
1.991 2.4387 154.81 153.82 in the direction of the applied field, leading to the positive magnetiza-
tion in the entire temperature range of measurement (Fig. 2b). It is also
speculated that Eu3+ spins do not contribute in the negative magne-
S = 2(a − c )/(a + c ) [41] was calculated with S = 0.035. As stated tization otherwise the same phenomenon could have been observed in
earlier, the ionic size of Eu3+ ion is smaller than those of La3+ and Sm3+ pristine EuCrO3 compound as well. Hence the negative magnetization
ions, therefore, the value of ‘t’ would be the lowest whereas ‘S’ would be behaviour is attested because of the substitution of Mn-ions only like in
the highest for ECMO compound as compared to LCMO and SCMO Mn-doped LaCrO3 and SmCrO3 chromites [19,20]. In the negative
compounds. These factors would lower the Neel temperature of the magnetization region, for MFC data, there is an anomaly as the
ECMO compound as explained later. magnetization changes slope close to 40 K like in MZFC graph. This
temperature is known as the spin reorientation transition temperature
3.2. Magnetization reversal and spin reorientation (TSR). There is a change in the easy magnetization direction and the
corresponding spin structure from Γ4(c-axis) to collinear Γ2(a-axis) at
The magnetization versus temperature (M-T) curves of the ECMO TSR. The spin reorientation transition in ECMO compound occurs due
compound taken in ZFC and FC modes under 200 Oe magnetic field to the presence of highly magnetic anisotropic Jahn Teller active Mn3+
from 2 to 300 K are shown in Fig. 2a. Both the curves almost coincide ion at Cr3+ sites. The magnetic interaction energy in such systems
with each other at high temperatures while keeping small but positive consists of isotropic Heisenberg exchange term causing antiferromag-
magnetization value which resembles a paramagnetic behaviour. A netic ordering, interaction of magnetic moments with applied magnetic
paramagnetic-antiferromagnetic transition i.e., TN is noticed around field, the antisymmetric Dzyloshinsky-Moriya (DM) interaction and the
160 K. It is worthwhile to mention here that TN for pristine EuCrO3 is ~ last term due to magnetocrystalline anisotropy energy. In compounds
181 K [31–33]. The decrease in TN in the present compound may be like the present one where a highly magnetic anisotropic ion is present,
attributed to the weakening of antiferromagnetic interaction among the last term dominates over others and causes a decrease in magnetic
Cr3+ ions and development of ferromagnetic double exchange interac- energy and the ensuing spin reorientation transition. Mn doping has
tion between Cr3+ (t2 g3eg0) and Mn3+ (t2 g3eg1) ions via oxygen ions. TN been shown to decrease the Neel transition temperature whereas an
of the ECMO compound is the lowest among ECMO, LCMO and SCMO increase in TSR is reported with increase in Mn-content [43].
compounds since it depends upon the ionic size of the rare-earth ion In order to get an estimate of the internal field produced by the
present and here Eu3+ ion has the smallest size [19,20]. Below TN, WFM component of Cr3+ ions the M-T curve at 200 Oe field in FC
magnetization starts increasing with a clear bifurcation between MZFC mode was further fitted to the following equation [44]:
and MFC curves. While MFC possesses higher value as compared to
C (HI + H )
MZFC, however, the former develops a hump at Tmax = 120 K with Mmax M = MCr +
T−θ (1)
~ 0.25 emu/g and thereafter it starts decreasing. On the other hand,
MZFC remains almost constant up to ~ 40 K. Below this temperature, where M, MCr, C, HI, H and θ stand for the total magnetization, weak
MZFC decreases rapidly. Both MZFC and MFC curves cross zero FM component of canted Cr3+ ions, a Curie constant, an internal field
magnetization at slightly different temperatures and become negative. from Cr3+ ion, an applied field and a Weiss temperature. The fitting is
The temperature where the magnetization changes polarity is known as shown in Fig. 2c (solid line), from where the values of Mcr, HI and θ
compensation temperature (Tcomp). The small difference in the com- were 0.536 emu / g, − 343 Oe and − 26 K, respectively. The negative
pensation temperatures between ZFC and FC data may be due to the value of internal field confirms the assumption that it is opposite to the
random distribution of net moments in the ZFC mode and preferred applied field and its value being larger than the applied magnetic field
orientation along the external field in FC mode. Moreover, it is (200 Oe) allows the spins of ions to get aligned antiparallel to Cr3+ ions.
meaningful to comment here that negative magnetization was never Fig. 2c also illustrates the inverse of the DC magnetic susceptibility
reported in pristine EuCrO3 compound. Therefore, the present ECMO against temperature (χ−1-T). The positive peak ~ 50 K corresponds to
compound clearly demonstrates the effect of Mn doping in tailoring the the compensation temperature whereas the dip ~ 40 K indicates the
magnetic behaviour of Eu-chromites. Further, the materials with spin reorientation transition TSR. The inverse of susceptibility varies
flipping magnetization not by the applied field rather by temperature linearly with temperature in the paramagnetic region. The fitting of
are very much suitable for thermomagnetic devices. The reason for the Curie–Weiss law, i.e., χ = C /(T −θW ), where C is Curie constant and θW
appearance of the negative magnetization in the present Mn-doped is Curie-Weiss temperature, to the experimental data is shown by a
EuCrO3 compound is as follows: the AFM nature and random solid line. The observed value of Curie constant ‘C’ obtained from the
distribution of the two magnetic ions (Cr3+ and Mn3+) at the same fitting is 0.0298 which is higher than that for pristine ECO compound
crystallographic site in ECMO may lead to the possible formation of Cr- (0.0217) [35]. The difference could be ascribed to the contribution of

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S. Kumar et al. Physica B 519 (2017) 69–75

Fig. 2. (a) ZFC and FC magnetization curves measured at 200 Oe, insets show the magnetization schemes above and below Tcomp, (b) ZFC and FC curves measured at 1 kOe and
2.5 kOe, inset depicts magnetization scheme at higher fields, (c) FC data (left side) fitted with Eq. (1) while the right side shows the reciprocal of dc magnetic susceptibility χ −1 versus
temperature at 200 Oe (the Solid line represents a Curie Weiss-type fit), (d) Relative irreversible magnetization.

Mn3+ ions magnetic moment to the effective magnetic moment. (‘C’ is clusters along the applied field direction. As a consequence of this, the
proportional to the square of effective magnetic moment). The calcu- magnetic irreversibility decreases. Thus, the decrease in magnetic
lated effective magnetic moment μeff (cal ) is 7.73 μB/f.u. and the Curie– irreversibility and negative magnetization with increasing external
Weiss temperature is about − 415 K. By using the relation magnetic field seem to be mutually correlated.
Mn 2
μeff (cal ) = Eu 2
(μeff ) +x (μ ) +(1 − x )(μCr
eff
Mn
)2 and considering μeff = 4.9 μB
eff
3.3. Magnetic hysteresis (M-H) loops
(+3 state) and μCr
eff
= 3.87 μB (+3 state), μeff
Eu
corresponding to Eu3+ ion
comes out to be 6.58 μB which is by far larger than the experimentally
The isothermal magnetization M-H curves recorded in ZFC mode at
observed value of Eu3+ equal to 3.4 μB albeit theoretical value is zero
different temperatures from 2 to 180 K are shown in Fig. 3. The sample
[45]. The difference was explained by Taheri et al. by considering the
was demagnetized every time after each measurement before taking the
weakly temperature dependent Van Vleck susceptibility of Eu3+ ions
next measurement. The loops are symmetrically closed like square
and its further enhancement by polarization of Eu3+ ions by Cr3+ ions
without any saturation. Such behaviour is attributed to the coexistence
[34]. The value of μeff and θW for the ECMO compound are greater than
of weak ferromagnetic (WFM) and antiferromagnetic components. The
those reported for undoped ECO compound by Deng et al. [35] which is
magnetization increases linearly for all the isothermal M-H curves at
clearly due to the doping of Mn3+ ions.
higher magnetic field. Therefore, the high-field part of the M-H curves
The bifurcation between the ZFC and FC curves below TN is known
evolution can be represented as M (H ) = χAFM H +Ms . Here χAFM H is the
as magnetic irreversibility and the temperature dependence of relative
antiferromagnetic contribution and Ms is the saturation magnetization
irreversible magnetization can be determined quantitatively using the
ΔM M −M of the weak ferromagnetic phase [48]. The low field WFM contribution,
relation M = FCM ZFC [46]. The temperature variation of ΔM for
ZFC ZFC MZFC Ms at different temperatures can be calculated by subtracting the high
different values of applied magnetic field is shown in Fig. 2d. All curves field linear AFM contribution from the total magnetization as shown in
pass through the compensation temperature. Broad positive peak of the inset of Fig. 3 at 2 K. The coexistence of FM and AFM states
large magnitude at T > Tcomp and negative peak (− 2.7) at T < Tcomp validates the canted antiferromagnetic state below the TN in the present
are observed at 200 Oe field. Generally, the maximum negative value of sample. The hysteresis behaviour apparently disappears above TN,
relative irreversible magnetization in orthochromites is found to be in indicating the phase transition at TN. While exchange bias effect
the range of ~ − 2 to − 9 [47]. Further, gradual suppression of relative (asymmetric hysteresis loop) was reported by Bora et al. [19] and
irreversibility with increase in applied field can be noticed. This is Deng at al. [35] in Mn doped LaCrO3 and Ca-doped EuCrO3 com-
understood on the fact that at higher values, the applied field over- pounds respectively, its absence in the present case may be attributed
comes the internal field resulting in the rotation of Mn-Cr ordered to the fact that they carried out the measurements in field cooled

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S. Kumar et al. Physica B 519 (2017) 69–75

Table 2
Magnetic entropy change and relative cooling power at various applied magnetic field.

HMax (kOe) -ΔSMax (J kg−1 K−1) RCP (J kg−1)

10 0.281 9.70
30 1.065 46.69
50 1.882 94.20
60 2.804 145.15
90 3.778 215.22

where average temperature Tav [ = (Tj+ Tj+1)/2] from the two magne-
tization isotherms measured at Tj and Tj+1 in a magnetic field changing
by ∆H = HF - HI at a constant step δ H. While δT = Tj+1–Tjis the
temperature difference between the two isotherms, n is the number of
points measured for each of the two isotherms with the magnetic field
changing from H1 = HI to Hn = HF at δ H = ∆H /(n − 1). Further
δMi = [M (Tj +1) − M (Tj ) ]is the difference in the magnetization at Tj+1
i i
and Tj for each magnetic field step from 1 to n. It is worthwhile
Fig. 3. Magnetization versus magnetic field at different temperatures. Inset shows initial mentioning here that the sign of -∆S provides information about the
M-H curve at 2 K, the AFM and the extracted WFM contribution.
magnetic transition [52]. For a ferromagnetic (FM) transition, a
positive value is obtained whereas an antiferromagnetic ordering
conditions whereas in the present case the loops were acquired in zero displays a negative value due to an orientation disorder of the magnetic
field cooled mode. sublattices. Therefore, it is customary to plot values of – ∆S against T
for different H values. For the present study, the data is presented in
3.4. Magnetocaloric effect Fig. 4b and it is found that – ∆S reaches a maximum value ~
3.788 J kg−1 K−1 near TSR under 90 kOe applied magnetic field. The
In order to further examine the performance of ECMO compound value of – ∆S at other fields are given in Table 2. The value of – ∆S
for magnetic refrigeration, M(H) data was acquired by varying the under 5 T applied magnetic field is almost eight times higher than that
magnetic field between 0 and 90 kOe. The data was assimilated reported for SmCrO3 chromites by Gupta et al. [53]. This value at 45 K
between 6 and 102 K temperature range at an interval of ΔT = 4 K is also almost equal to that observed by our earlier studies in
and plotted in Fig. 4a. Magnetic refrigeration is related to the MCE that SmCr0.85Mn0.15O3 orthochromite compound [20] and higher than that
is directly proportional to the slope of magnetization versus tempera- of the reported for TmCrO3 by K. Yoshi [3]. Thus, it is clear from the
ture at constant applied field [49]. The MCE of the polycrystalline above discussion that, higher value of magnetocaloric effect is observed
ECMO sample was evaluated by calculating two factors: one is near the spin reorientation temperature in the present compound.
magnetic entropy change with the variation of the external magnetic Again, in our recent studies we found five times higher value of – ∆S
field and another is relative cooling power (RCP). The magnetic under 5 T applied magnetic field for PrCr0.85Mn0.15O3 compound in
entropy change, ∆S (T )∆ H , can be calculated by using the following comparison to that of the present compound, but the spin reorientation
Maxwell equation [50]: temperature for the former was lower than observed for the present
HF ∂M (T , H ) compound [21]. Another important parameter for magnetic refrigera-
∆S (T )∆ H = ∫H I
(
∂T
)H dH tion is the relative cooling power (RCP), which we calculated for the
ECMO compound by the following expression [54]:
Generally, for ΔS calculation from a series of M-H curves, numer- T2
ical integration of the above Eq. by trapezoidal rule results [51]: RCP = ∫T 1
∆S (T )∆ H dT
n −1
δH
∆S (Tav )∆ H = (δM1+2 ∑ δMi + δMn ) where T1 and T2 are the low and high temperature limits in the
2δT i =2 (3) refrigeration cycle. It can be also estimated for each value of field

Fig. 4. (a) M- H curve different temperature region, (b) Magnetic entropy change as a function of temperature for different magnetic field values.

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S. Kumar et al. Physica B 519 (2017) 69–75

imperative to study the effect of different elements like Mn and Fe


substitution with varying concentration on the magnetic and thermal
properties of Eu-chromites, therefore, such studies are under progress.

4. Conclusions

Effect of 15% Mn substitution on the structural, magnetic and


magnetocaloric properties of Mn doped EuCrO3 (ECO) chromite have
been investigated. Lattice volume was found to increase without
inducing any structural transition. Neel temperature of the pristine
compound showed a decrease with the Mn-substitution. Magnetization
reversal and spin reorientation transition were observed in the studied
sample while such effects were never reported in the pristine sample.
Magnetic refrigerating performance of the compound was measured
through the magnetic entropy change and relative cooling power. Near
the spin reorientation transition temperature, the magnetic entropy
change was maximum and equal to 3.788 J kg−1 K−1 under 90 kOe field
with 215.22 J kg−1relative cooling power. The results attest the effec-
Fig. 5. Normalized entropy change for different applied magnetic fields (10–90 kOe) at
TSR.
tiveness of Mn-substitution in tailoring the magnetic and magnetoca-
loric properties of Eu-orthochromites.
variation by the product of the maximum magnitude of |ΔS max | and its
Acknowledgements
fullwidth at half maximum ( ΔTFWHM ), i.e.
≈| ΔS max | × ΔTFWHM The author S. K. would like to thank University Grant Commission,
−1 New Delhi for providing Rajiv Gandhi National Fellowship (RGNF)
The maximum RCP is obtained ~ 215.22 J kg at 90 kOe magnetic
whereas I. C. acknowledges the financial support from FCT, Portugal
field (Table 2).
through SFRH/BPD/81032/2011. The authors would also like to thank
We also explored the universal behaviour for the entropy change in
Council of Scientific and Industrial Research networking projects
ECMO compound with second order phase transition which can be
SURE-CSC0132 and INTELCOAT-CSC0114 for partially supporting
recognized by scaling the axes appropriately. The universal behaviour
this work.
was explored by rescaling the axes for a universal curve, i.e. all ΔSM (T)
curves were normalized with their maximum entropy change (ΔSMpk),
References
respectively by equation [53,55]:
⎧ (T − TSR) [1] K. Yoshii, A. Nakamura, Reversal of magnetization in La0.5Pr0.5CrO3, J. Solid State
⎪− (T − T ) , T ≤ TSR Chem. 155 (2000) 447–450.
θ = ⎨ (TR−1 T SR [2] K. Yoshii, Magnetization reversal in TmCrO3, Mater. Res. Bull. 47 (2012)
⎪ SR )
, T > TSR
⎩ (TR2 − TSR) 3243–3248.
[3] V.S. Bhadram, B. Rajeswaran, A. Sundaresan, C. Narayana, Spin-phonon coupling
hereTR1 and TR2 are the reference temperatures where ΔS equals in multiferroic RCrO3(R-Y, Lu, Gd, Eu, Sm): a Raman study, Eur. Phys. Lett. 101
(2013) 17008.
ΔSMpk/2. [4] P. Gupta, R. Bhargava, R. Das, P. Poddar, Static and dynamic magnetic properties
The two reference temperatures TR1 and TR2, are needed to and effect of surface chemistry on the morphology and crystallinity of DyCrO3
characterize the entropy change, where TR1 < TSR and TR2 > TSR . The nanoplatelets, RSC Adv. 3 (2013) 26427–26432.
[5] P. Gupta, R. Bhargava, P. Poddar, Colossal increase in negative magnetization,
transformed curves of ECMO under different field values at ~ TSR are exchange bias and coercivity in samarium chromite due to a strong coupling
plotted in Fig. 5, from where it can be noticed that all the curves between Sm3+–Cr3+ spins sublattices, J. Phys. D: Appl. Phys. 48 (2015) 025004.
collapse into a single curve in temperature regions near to the ordering [6] H.J. Zhao, J. Íñiguez, X.M. Chen, L. Bellaiche, Origin of the magnetization and
compensation temperature in rare-earth orthoferrites and orthochromites, Phys.
temperature (θ = 0). This attests our treatment of data according to
Rev. B 93 (2016) 014417.
second order phase transition theory for ECMO compound. However, [7] J.R. Sahu, C.R. Serrao, N. Ray, U.V. Waghmare, C.N.R. Rao, Rare earth chromites:
as one moves away from the ordering temperature where ΔSmax is a new family of multiferroics, J. Mater. Chem. 17 (2007) 42–47.
observed, breakdown can be observed in the curve which is acceptable [8] B. Rajeswaran, D.I. Khomskii, A.K. Zvezdin, C.N.R. Rao, A. Sundaresan, Field-
induced polar order at the Néel temperature of chromium in rare-earth ortho-
as scaling laws need not hold far away from the spin reorientation chromites: interplay of rare-earth and Cr magnetism, Phys. Rev. B 86 (2012)
transition [52]. 214409.
Finally, the magnetocaloric data on the pristine EuCrO3 compound [9] B. Raveau, M.M. Seikh, Impact of crystal chemistry upon spin orientation
transitions in magnetic perovskites, Z. Anorg. Allg. Chem. 640 (2014) 2649–2657.
was not reported so far in the literature and thus we could not compare [10] R. Saha, A. Sundaresan, C.N.R. Rao, Novel features of multiferroic and magneto-
its results with the present one. Further, there was no spin reorienta- electric ferrites and chromites exhibiting magnetically driven ferroelectricity,
tion transition reported in the pristine EuCrO3 compound, but, the Mater. Horiz. 1 (2014) 20–31.
[11] K.R.S.P. Meher, A. Wahl, A. Maignan, C. Martin, O.I. Lebedev, Observation of
present compound showed the spin reorientation transition close to electric polarization reversal and magnetodielectric effect in orthochromites: a
40 K. Like for the present studied compound and the data reported in comparison between LuCrO3 and ErCrO3, Phys. Rev. B 89 (2014) 144401.
the literature, it is our assertion that magnetocaloric properties are [12] A. McDannald, L. Kuna, M.S. Seehra, M. Jain, Magnetic exchange interactions of
rare-earth substituted DyCrO3 bulk powders, Phys. Rev. B 91 (2015) 224415.
higher near the spin reorientation transition, therefore the Mn-doped [13] S.M. Yusuf, A. Kumar, J.V. Yakhmi, Temperature and magnetic-field-controlled
EuCrO3 can be expected to demonstrate better results than the pristine magnetic pole reversal in a molecular magnetic compound, Appl. Phys. Lett. 95
one. This assumption is further validated by our recent study in Mn- (2009) 182506.
[14] I.L. Prejbeanu, M. Kerekes, R.C. Sousa, H. Sibuet, O. Redon, B. Dieny,
doped SmCrO3 compound where we observed superior magnetocaloric
J.P. Nozières, Thermally assisted MRAM, J. Phys.: Condens. Matter 19 (2007)
properties as compared to the pristine SmCrO3 compound [20]. The 165218.
novelty of the present work lies in the induction of magnetization [15] Y. Cao, S. Cao, W. Ren, Z. Feng, S. Yuan, B. Kang, Bo Lu, J. Zhang, Magnetization
reversal in Eu-orthochromites with Mn-substitution, observation of switching of rare earth orthochromite CeCrO3, Appl. Phys. Lett. 104 (2014)
232405.
spin reorientation transition and magnetocaloric effect better and at [16] P. Gupta, P. Poddar, Temperature and magnetic field-assisted switching of
higher temperature than that reported for other chromites. It is also

74
S. Kumar et al. Physica B 519 (2017) 69–75

magnetization and observation of exchange bias in YbCrO3 nanocrystals, Inorg. of EuCrO3 nanopowders, Phys. Rev. B 93 (2016) 104414.
Chem. 54 (2015) 9509–9516. [35] D. Deng, X. Wang, J. Zheng, X. Qian, D. Yu, D. Sun, C. Jing, B. Lu, B. Kang, S. Cao,
[17] S. Geller, Crystallographic studies of perovskite-like compounds. IV. Rare earth J. Zhang, Phase separation and exchange bias effect in Ca doped EuCrO3, J. Mag.
scandates, vanadites, galliates, orthochromites, Acta Crystallogr. 10 (1957) Magn. Mater. 395 (2015) 283–288.
243–248. [36] H.M. Widatallah, T.M. Al-Shahumi, Z. Klencsar, M. Pekala, A.M. Gismelseed,
[18] H.T. Stokes, E.H. Kisi, D.M. Hatch, C.J. Howard, Group-theoretical analysis of I.A. Al-Omari, A.D. Al-Rawas, D. Seifu, Structural, magnetic and 151Eu Mössbauer
octahedral tilting in ferroelectric perovskites, Acta Crystallogr. B 58 (2002) studies of mechanosynthesized nanocrystalline EuCr1−xFexO3 particles, Acta Mater.
934–938. 61 (2013) 4461–4473.
[19] T. Bora, S. Ravi, Sign reversal of magnetization and exchange bias field in [37] B.T. Kilbourn, A Lanthanide LanthologyolycorpInc, White Plains, New York, 1993.
LaCr0.85Mn0.15O3, J. Appl. Phys. 114 (2013) 183902. [38] K. Tsushima, I. Takemura, S. Osaka, Weak-ferromagnetism in EuCrO3, Solid State
[20] S. Kumar, I. Coondoo, M. Vasundhara, A.K. Patra, A.L. Kholkin, N. Panwar, Commun. 7 (1969) 71–73.
Magnetization reversal behavior and magnetocaloric effect in SmCr0.85Mn0.15O3 [39] R.D. Shannon, Revised effective ionic radii and systematic studies of interatomic
chromites, J. Appl. Phys. 121 (2017) 043907. distances in halides and chalcogenides, Acta Cryst. A 32 (1976) 751–767.
[21] S. Kumar, I. Coondoo, M. Vasundhara, S. Kumar, A.L. Kholkin, N. Panwar, [40] J.R. Carvajal, Recent advances in magnetic structure determination by neutron
Structural, magnetic, magnetocaloric and specific heat investigations on Mn doped powder diffraction, Physica B 192 (1–2) (1993) 55–69.
PrCrO3 orthochromites, J. Phys.: Condens. Matter 29 (2017) 195802. [41] T.S. Chan, R.S. Liu, C.C. Yang, W.H. Li, Y.H. Lien, C.Y. Huang, J.F. Lee, Chemical
[22] L.H. Yin, Y. Liu, S.G. Tan, B.C. Zhao, J.M. Dai, W.H. Song, Y.P. Sun, Multiple size effect on the magnetic and electrical properties in the (Tb1−xEux)MnO3 (0 ≤ x
temperature-induced magnetization reversals in SmCr1−xFexO3 system, Mater. Res. ≤1.0)system, J. Phys. Chem. B 111 (2007) 2262–2267.
Bull. 48 (2013) 4016–4021. [42] J. Kanamori, Superexchange interaction and symmetry properties of electron
[23] Y. Ren, T.T.M. Palstra, D.I. Khomskii, A.A. Nugroho, A.A. Menovsky, orbitals, J. Phys. Chem. Solids 10 (1959) 87–98.
G.A. Sawatzky, Magnetic properties of YVO3 single crystals, Phys. Rev. B62 (2000) [43] Y. Sundarayya, P. Mandal, A. Sundaresan, C.N.R. Rao, Mossbauer spectroscopic
6577. study of spin reorientation in Mn-substituted yttrium orthoferrites, J. Phys.:
[24] A.V. Mahajan, D.C. Johnston, D.R. Torgeson, F. Borsa, Magnetic properties of Condens. Matter 23 (2011) 436001.
LaVO3, Phys. Rev. B 46 (1992) 10966. [44] A.H. Cooke, D.M. Martin, M.R. Wells, Magnetic interactions in gadolinium
[25] J. Hemberger, S. Lobina, H.A. Krug von Nidda, N. Tristan, V. Yu Ivanov, orthochromite GdCrO3, J. Phys. C: Solid State Phys. 7 (1974) 3133.
A.A. Mukhin, A.M. Balbashov, A. Loidl, Complex interplay of 3d and 4f magnetism [45] C. Kittel, Introduction to solid state physics, 2004, p. 306.
in La1−xGdxMnO3, Phys. Rev. B 70 (2004) 024414. [46] B.B. Dash, S. Ravi, Sign reversal of magnetization in Mn substituted SmCrO3, J.
[26] I.O. Troyanchuk, V.A. Khomchenko, G.M. Chobot, A.I. Kurbakov, A.N. Vasil’ev, Mag. Magn. Mater. 405 (2016) 209–213.
V.V. Eremenko, V.A. Sirenko, M. Yu. Shvedun, H. Szymczak, R. Szymczak, Spin- [47] N. Sharma, B.K. Srivastava, A. Krishnamurthy, A.K. Nigam, Magnetic behaviour of
reorientational transitions in low-doped Nd1−xCaxMnO3 manganites: the evidence the orthochromite La0.5Gd0.5CrO3, Solid State Sci. 12 (2010) 1464–1468.
of an inhomogeneous magnetic state, J. Phys. Condens. Matter 15 (2003) 8865. [48] A. Durán, A.M.A. López, E.C. Martínez, M.G. Guaderrama, E. Moran, M.P. Cruz,
[27] I. Dzyaloshinsky, A thermodynamic theory of “weak” ferromagnetism of anti- F. Fernández, M.A.A.- Franco, Magneto-thermal and dielectric properties of
ferromagnetics, J. Phys. Chem. Solids 4 (1958) 241. biferroic YCrO3 prepared by combustion synthesis, J. Solid State Chem. 183 (2010)
[28] T. Moriya, Anisotropic super-exchange interaction and weak ferromagnetism, Phys. 1863–1871.
Rev. 120 (1960) 91. [49] M.-H. Phan, S.-C. Yu, Review of the magnetocaloric effect in manganite materials,
[29] K. Yoshii, Magnetization reversal in TmCrO3, Mater. Res. Bull. 47 (2012) 3243. J. Mag. Magn. Mater. 308 (2007) 325–340.
[30] S. Yin, M. Jain, Enhancement in magnetocaloric properties of holmium chromite by [50] A.H. Morrish, The Physical Principles of Magnetism, Wiley, New York, 1965
gadolinium substitution, J. Appl. Phys. 120 (2016) 043906. (Chapter 3).
[31] M. Taheri, R.K. Kremer, S. Trudel, F.S. Razavi, Exchange bias effect and glassy-like [51] V.K. Pecharsky, K.A. Gschneidner Jr., Magnetocaloric effect from indirect mea-
behavior of EuCrO3 and CeCrO3 nano-powders, J. Appl. Phys. 118 (2015) 124306. surements: magnetization and heat capacity, J. Appl. Phys. 86 (1999) 565.
[32] J.M.M. Ramirez, H.V.S. Pessoni, A. Franco Jr., F.L.A. Machado, Synthesis of [52] M.H. Phan, N.A. Frey, M. Angst, J. de Groot, B.C. Sales, D.G. Mandrus, H. Srikanth,
europium orthochromites (EuCrO3) nanoparticles by a combustion reaction Complex magnetic phases in LuFe2O4, Solid State Commun. 150 (2010) 341–345.
method, J. Alloy. Compd. 690 (2017) 315–320. [53] P. Gupta, P. Poddar, Study of magnetic and thermal properties of SmCrO3
[33] H.M. Widatallah, S.H. Al-Harthi, C. Johnson, Z. Klencsar, A.M. Gismelseed, polycrystallites, RSC Adv. 6 (2016) 82014–82023.
E.A. Moore, A.D. Al Rawas, C.I. Wynter, D.E. Brown, Formation, cationic site [54] A. McDannald, M. Jain, Magnetocaloric properties of rare-earth substituted
exchange and surface structure of mechanosynthesized EuCrO3 nanocrystalline DyCrO3, J. Appl. Phys. 118 (2015) 043904.
particles, J. Phys. D: Appl. Phys. 44 (2011) 265403. [55] V. Franco, J.S. Blázquez, B. Ingale, A. Conde, The magnetocaloric effect and
[34] M. Taheri, F.S. Razavi, Z. Yamani, R. Flacau, P.G. Reuvekamp, A. Schulz, magnetic refrigeration near room temperature: materials and models, Ann. Rev.
R.K. Kremer, Magnetic structure, magnetoelastic coupling, and thermal properties Mater. Res. 42 (2012) 305–342.

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