Structural, magnetic and magnetocaloric investigations in Pr0.67Ba0.22Sr0.11Mn1-xFexO3 (0 ≤ x ≤ 0.15) manganite oxide

Accepted Manuscript Structural, magnetic and magnetocaloric investigations in Pr0.67Ba0.22Sr0.11Mn1xFexO3 (0 ≤ x ≤ 0.15) manganite oxide K. Snini, F. Ben Jemaa, M. Ellouze, E.K. Hlil PII:

S0925-8388(17)34505-X

DOI:

10.1016/j.jallcom.2017.12.309

Reference:

JALCOM 44395

To appear in:

Journal of Alloys and Compounds

Received Date: 5 October 2017 Revised Date:

14 December 2017

Accepted Date: 25 December 2017

Please cite this article as: K. Snini, F. Ben Jemaa, M. Ellouze, E.K. Hlil, Structural, magnetic and magnetocaloric investigations in Pr0.67Ba0.22Sr0.11Mn1-xFexO3 (0 ≤ x ≤ 0.15) manganite oxide, Journal of Alloys and Compounds (2018), doi: 10.1016/j.jallcom.2017.12.309. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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Structural, magnetic and magnetocaloric investigations in Pr0.67Ba0.22Sr0.11Mn1-xFexO3 (0 ≤ x ≤ 0.15) manganite oxide. K. Snini1,, F. Ben Jemaa1, M. Ellouze1, E. K. Hlil2. Laboratoire des Matériaux Multifonctionnels et Applications (LMMA), Faculté des Sciences

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1

de Sfax (FSS), Université de Sfax, Route de Soukra, km 3.5, B.P.1171, 3000 Sfax, La Tunisie. 2

Institut Néel, CNRS et Université Joseph Fourier, BP 166, F-38042 Grenoble Cedex 9,

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France. Abstract

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In the present work, we have investigated the structural, magnetic and magnetocaloric properties of Pr0.67Ba0.22Sr0.11Mn1-xFexO3 (0 ≤ x ≤ 0.15) manganites oxides. The compounds were elaborated using the conventional solid-state reaction. X-ray diffraction (XRD) at room temperature were used to carry out the structural properties. The magnetic and the

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magnetocaloric effect properties were explored using magnetization measurements at different parameters such as changing temperature or the applied magnetic field. XRD results indicate that all our compositions crystallized in the orthorhombic structure with Pnma space

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group. Magnetic measurements as a function of temperature, M (T), under an applied

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magnetic field of 0.05 T show that all the synthesis compounds present a paramagnetic (PM) – ferromagnetic (FM) transition with decreasing temperature. Arrott plots analysis reveals that our materials exhibit a second order magnetic phase transition. The magnetic entropy change |∆ | was calculated using Maxwell relation. The maximum values of the magnetic  entropy change (|∆ |) for x = 0.00, 0.05, 0.10 and x = 0.15 are found to be 4.72, 1.90, 1.45

and 0.83 J kg−1K−1, respectively, which corresponds to relative cooling power (RCP) about 218, 175, 122 and 79 Jkg−1 under a magnetic field change of 5T.

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ACCEPTED MANUSCRIPT Keywords: Manganites; X-ray diffraction; Rietveld refinement; Magnetization; Relative cooling power. *Corresponding author: Prof. Dr. Mohamed Ellouze

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E-mail : [email protected]

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Phone: +21698414707

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ACCEPTED MANUSCRIPT 1. Introduction The manganites T1-xRxMnO3 (T = rare-earth elements and R = alkaline earth metals) are well-known giant magnetoresistance perovskite with ferromagnetic order. As we know the ferromagnetic character of these compounds is principally due to double exchange (DE)

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between Mn3+ and Mn4+ ions [1–4]. Many works have been done by means of doping at Mn site by other transition elements in T1-xRxMnO3 [5, 6]. It changes the Mn3+-O-Mn4+ network and in turn widely affects their magneto-transport properties as well as MCE [3-6]. Leung et

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al. [7] investigated the effect of Fe doping in the La0.7Pb0.3Mn1-xFexO3 sample. It has been proven [8] that iron enters as high spin Fe3+ and in view of the almost identical ionic radii of

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Mn3+ and Fe3+ the lattice distortion effects can almost be neglected. As we know, the ''eg'' spin-up orbital’s are completely occupied, which prevent electron hopping from Mn to Fe, that's why random substitution of Mn by Fe ions crushes DE but leaves antiferromagnetic (AF) superexchange interactions undisturbed [9].

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In the last several years, extensive investigation have been done by doping at B-site by Various Works. They have proposed that the insertion of other transition metal elements, which exhibit the not similar electronic configuration to Mn-site, should lead to considerable results related with the electronic configuration unsuitably between manganese and the other

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substitute magnetic ions. That is the reason why, the substitution of manganese by iron ions can give rise to considerable modifications in the magnetic and transport properties of these

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compounds[10–12]. In this work, we have done polycrystalline Pr0.67Ba0.22Sr0.11Mn1-xFexO3 by the Ceramic method. A lot of scientific causes can make the investigation in this domain more and more important and which would open the possibilities to explore the magnetic properties of those materials. We can cite as examples the two important causes which are, first of all both manganese and iron have the same ionic radii. The second cause is that the crystalline structure is not modified by the substitution of Mn by Fe (II). The perovskite type manganite La0.7Sr0.3Mn1-xFexO3 has a large bandwidth, that doesn’t have nearly any phenomena like electron–phonon interactions characteristic of narrow-bandwidth materials. Therefore, lattice effects can be neglected and effects due to the variation in electronic

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ACCEPTED MANUSCRIPT structure become accessible. Consequently, Iron can be employed as a control parameter in order to change only the transport properties and magnetic of these manganites.

2. Experimental details Pr0.67Ba0.22Sr0.11Mn1-xO3 (compounds were synthesized using the conventional solid-state

99% in the desired proportion according to the reaction: 0.11Pr6O11 + 0.22BaO2+ 0.11SrO2 + x/2Fe2O3 + (1-x) MnO2

Pr0.67Ba0.22Sr0.11Mn1- xFexO3 +

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δO2 (1)

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reaction by mixing Pr6O11, BaO2, SrO2, MnO2 and Fe2O3 precursors with purities higher than

The started precursors were intimately mixed in an agate mortar. Then the powders were

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pressed into pellets (about 1mm in thickness) and sintered at 800, 1000, 1200 and 1300°C for 24h with intermediate regrinding and re-pelletizing to ensure a better crystallization. Finally, those pellets were slowly cooled to room temperature in air. For all samples, phase purity and cell parameters were determined by powder X ray diffraction, recorded at room temperature

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on a Panalytical X’PERT Pro diffractometer, using θ/2θ Bragg–Brentano geometry with diffracted beam monochromatized CuKα radiation. The diffraction patterns were collected by steps of 0.017 over the angle range 10–70°. Structural analyses were checked by the Rietveld

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method using the FullProf program [13, 14].

Magnetization measurements versus temperature, M(T), in the range 5-400 K and versus

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magnetic applied field, M(µ 0H), were carried out using a Vibrating Sample Magnetometer (VSM). Magnetocaloric effect (MCE) was estimated based on the magnetization measurements versus magnetic applied field up to 5T at several temperatures.

3. Results and discussion 3.1. Structural properties To check their structures and phases purities, X-ray diffraction (XRD) measurements for all our samples were carried out at room temperature. Fig. 1 represent the Rietveld refinement of 4

ACCEPTED MANUSCRIPT powder X-ray diffraction patterns of Pr0.67Ba0.22Sr0.11Mn1-xFexO3 for x=0 and x=0.05 as example. A single phase was observed for all materials without any detectable impurities. The results reveal that our compounds crystallized in the orthorhombic structure with Pnma space group. The atomic positions are taken at 4c (x, 0.25, z) for (Pr, Ba and Sr), 4b (0.5, 0, 0) for

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(Mn and Fe), 4c (x, 0.25, z) for O1 and 8d (x, y, z) for O2. The structural parameters, the goodness of the fit indicator and the agreement factors (Braggs factor RBragg and structure factor RF) are summarized in Table. 1. From this table, it is clear that unit cell volume of our

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samples increases from 234.243 Å3 for x = 0 to 234.540 Å3 for x = 0.15. As the Mn3+ ion and the Fe3+ ion have the same ionic radii (0.645 Å). The ionic radii were taken according to

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Shannon [15]. the increase in volume can be related to the increase of angles. Those results show an important accord with previous results reported in the literature [16, 17]. Lattice distortions may be caused by either Jan-Teller effect inherent to the Mn3+ high spin state, effect causing a distortion of MnO6 octahedra. It is important to calculate the

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tolerance factor of Goldschmidt (t), given by:

=

  

(2)

√ (    )

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where 〈 rA〈 ; 〈 rB〈 , and rO are the average ionic radius of the A-site, B and O ions, respectively. The calculated tolerance factors for the samples were found to be t= 0.9168. The

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values of t (Table 1) have been estimated and they are within the range of stable perovskite structure.

The crystallite size DSC was estimated from XRD line broadening using Scherrer equation:

 =





(3)

We have equally estimated the crystallites size DWH of our compound by analyzing the widening of X-ray diffraction peaks, using the Williamson–Hall approach. The WilliamsonHall (W-H) equation is defined by [18]: 5

ACCEPTED MANUSCRIPT    =  ⁄!"# + &' () 

(4)

Where where λ is the wavelength of CuKα radiation (1.5406Å), θ is the diffraction angle of the peaks β is the full width at half maximum of the Bragg peaks.and ' = *+⁄+ is a coefficient related to strain effect on the crystallites. The value of ε is calculated from the

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slope of β cosθ θ vs. 4 sinθ θ plot (Fig. 2). The particle size DWH was calculated from the intercept with vertical axis (Kλ/DWH=intercept). The calculated values of crystallites sizes DSC and DWH are summarized in Table. 1. The difference between the calculated crystallites

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sizes using the two methods can be related to the fact that the broadening effect due to strain

3.2. Magnetic properties

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is completely excluded in Scherrer technique.

Magnetization measurements versus temperature in the range 5–400 K and in a magnetic applied field of 0.05 T reveals that all our elaborated compounds exhibit a paramagnetic (PM)

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to ferromagnetic (FM) transition with decreasing temperature (Fig.3). With increasing Fe content, the Curie temperature TC decreases from 216 K for x = 0 to 56K for x = 0.15. The decrease of The Curie temperature TC can be explained by the increase in the number of Fe3+-

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O-Fe3+, which induces a weakening of the ferromagnetism. In addition, this evolution can be explained by the fact that the presence of iron weakens the double exchange interactions to

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the profit of the super exchange ones in the complex Fe3+-O-Mn3+. In addition, the presence of iron modifies the Mn-O-Mn angles and the Mn/Fe-O distances thus decreasing the Curie temperature. Similar evolution was found by Nassri et al. [19] and Zouari et al. [20] after substitution by iron in B-site. The Curies temperatures deduced from the minimum of dM/dT versus temperature curves (the inset of Fig.3) are listed in Table.2. Fig. 4 presents the inverse of susceptibility as function of the temperature, for the two samples x=0 and x=0.05, deduced from M (T) curve at 0.05 T and the fitting result according to the Curie -Weiss (CW) law given as bellow [21]: 6

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, (1) - − /0

where , = 23 μ 5 μ 677⁄8 5 is the Curie constant and 9 is the Curie-Weiss temperature. The Curie constant C and the Curie -Weiss temperature 9 knowledge provides access to the 60

60

μ677 = (8 5 ,)=:2μ; μ 5 <

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effective paramagnetic moment μ677 in the paramagnetic phase defined by:

(6)

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where: N is the Avogadro number, µB is the Bohr magneton and KB is the Boltzmann constant. Generally, the theoretical effective paramagnetic moment is calculated based on the

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following equation:





8 8 8 & μ>?6 677 = @;. BC μ677 (9D ) + (;. BC − ) μ677 () ) +  μ677 (E6 ) + ;. 81 μ677 () )

(7)

with µeff (9D 8 ) = 3.58µ B, µeff ()8 ) = 4.91µ B, µeff (768 ) = 5.92µ B and µeff ()& )

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=3.87µ B [22].

We can reveal from the results shown by Table 2 that the experimental values of µeff are larger than the theoretical ones confirming the existence of FM clusters in the paramagnetic

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state just above TC [23].

Our goal is to study the magnetic properties at low temperatures, so we have carried out the

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magnetization measurements as function of magnetic applied field up to 5T at several temperatures. The magnetization evolution vs. magnetic applied field at various temperature for x=0 and x=0.05 was plotted in Fig. 5. We can see clearly that the magnetization increased sharply at low magnetic fields (µ0H < 0.5 T) and then saturates for fields above 1 T, which confirms the existence of ferromagnetic state at low temperatures for all our compounds. In the other hand, we observe a linear behavior at high temperatures, presenting a sign of the paramagnetic state. In order to study the nature of magnetic phase transition, the Arrott plots given M2 vs. µ0H/M are plotted (Fig. 6) [24]. The order of the FM – PM transition has been 7

ACCEPTED MANUSCRIPT studied based on the Banerjee's criterion [25]. The Arrott curves have a positive slope witch indicate that our materials undergoes a second order FM–PM phase transition. The magnetocaloric effect (MCE) is an intrinsic characteristic of most magnetic materials and the coupling of the magnetic sublattice with the magnetic applied field induces it. The MCE

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can be calculated indirectly using the magnetization measurements versus magnetic applied field at several temperatures. According to The Maxwell thermodynamic equation, the MCE is given by [26]:

G G I = F I (J) GH G- H

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F

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where S is the magnetic entropy, M is the magnetization and H the magnetic applied field. After the integration of Eqs.8, the magnetic entropy change can be written as; ∆ (-, μ; H ) = L

Q; H

;

G M N OH (P) G- H

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If the magnetization measurements is performed at small discrete field and temperature intervals, ∆SM can be approximated as: ∆ (-, μ; H)= R

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(

(S (-(S , μ; H) −  ( (-( , μ; H) OH( (S;) -(S − -(

where Mi and Mi+1 are the magnetization values measured at µ0H, at Ti and Ti+1 temperatures,

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respectively.

Using the Maxwell thermodynamic equation, the magnetic entropy change was calculated for all our samples. The estimated |∆ | versus temperature of Pr0.67Ba0.22Sr0.11Mn1-xFexO3 for x=0 and x=0.05 is given in Fig. 7 (a-b). From the obtained curves, we can observe that our materials have a large magnetocaloric effect near Curie temperatures and the maximum of the |∆ | increases when µ 0H increase. The maximum values of the magnetic entropy change  (|∆ |) for x = 0.00, 0.05, 0.10 and x = 0.15 are found to be 4.72, 1.90, 1.45 and 0.83 Jkg− 1

K−1, respectively, under a magnetic field change of 5T. The relative cooling power (RCP) 8

ACCEPTED MANUSCRIPT values are a useful way to evaluate the samples according to their efficiency. It represents the area under the |∆ | versus temperature curves. It can be estimated by integrating the |* (-)| curves over the full width at half-maximum [27, 28]. The RCP is an important parameter to select magnetic refrigerants. It measures the heat transfer between hot and cold

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sources during a refrigeration cycle and it is calculated by the following expression:

 (-, μ; H ) × δ-EVH (SS) T,9 = −∆  where −∆ is the value of the maximum of the magnetic entropy change and δ-EVH is

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the full-width at half-maximum of |∆ |. The RCP values for x = 0.00, 0.05, 0.10 and x =

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0.15 are found to be 218, 175, 122 and 79 Jkg−1, respectively, under a magnetic field change of 5T. These results ensure that the currently investigated samples present good properties and parameters to be explored for magnetic refrigeration applications. We summarized in Table 3  and RCP values, in order to compare the results with the Curie temperature TC, −∆

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those reported in literature [10, 19, 20, 28, 29, 30].

From the variation of the specific heat as a function of the applied field, with a magnetic field variation from 0 to (µ0H)max, we can estimate the change of magnetic entropy [31]: GW∆ (-, μ; H)X (S ) G-

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∆,9 (-, μ; H) = ,9 (-, μ; H) − ,9 (-, ;) = -

Using the Equ.11, we have plotted ∆Cp (T, µ0H) as function of the temperature for x=0 and x=0.05 compounds at various magnetic applied field (Fig. 8). The value of ∆Cp changes from positive to negative near Curie temperature TC. The maximum/minimum values of ∆Cp are summarized in Table 3. 4. Conclusion To conclude our scientific studies, we investigated the effect of substitution of manganese by iron on the structural, magnetic and magnetocaloric properties of Pr0.67Ba0.22Sr0.11Mn19

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(0 ≤ x ≤ 0.15) manganites oxides. The desired samples were elaborated using the

conventional solid-state reaction. XRD analysis reveals that our materials crystallized in the orthorhombic structure with the Pnma space group. Magnetic measurements show that all samples exhibit a paramagnetic (PM) – ferromagnetic (FM) transition with decreasing

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temperature. The Curie temperature TC increased with increasing iron content. The Magnetic measurements show also that all materials present a second order PM–FM magnetic transition. The magnetocaloric effect study indicates that the investigated compounds have the

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appropriate properties to be suitable candidates to be used as refrigerants.

Acknowledgements:

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The Tunisian Ministry of Higher Education and Scientific Research supported this work.

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Insausti, T. Rojo, J. Phys. Rev. B 61 (2000) 9028. [9] J. Gutiérrez, F.J. Bermejo, J.M. Barandiara´n, S.P. Cottrell, P. Romano, C. Mondelli, J.R.

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Stewart, L. Ferna´ndez-Barquı´n, A. Pen˜a, J. Phys. Rev. B 73 (2006) 054433. [10] F. Ben Jemaa, S. Mahmood, M. Ellouze, E.K. Hlil, E. Halouani, I. Bsoul, M. Awawdeh,

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Solid State Sci. 37 (2014)121.

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ACCEPTED MANUSCRIPT [16] A. G. Souza Filho, J. L. B. Faria, I. Guedes, J. M. Sasaki, P. T. C. Freire, V. N. Freire, J. Mendes Filho, M. Xavier Jr, F. A. O. Cabral, J. H. de Araujo, J. A. P. da Costa, Phys. Rev. B 67 (2003) 052405. [17] J. Gutierrez, A. Pena, J. M. Barandiaran, T. Hernandez, J. L. Pizarro, L. Lezama, M.

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Alloys Compd. 688 (2016) 752. [22] B. D. Cullity, New York, (1972).

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[21] H. Omrani, M. Mansouri, W. Cheikhrouhou Koubaa, M. Koubaa, A. Cheikhrouhou, J.

[23] B. Martinez, V. Laukhin, J. Fontcuberta, L. Pinsard, A. Revcolevschi, Phys. Rev. B 66

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(2002) 054436.

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[25] S. K. Banerjee, Phys. Lett. 12 (1964) 16.

[26] R. D. Michael, J. J. Ritter, R. D. Shull, J. Appl. Phys. 73 (1993) 6946.

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[27] K. A. Gschneidner, V. K. Pecharsky, A. O. Tosko, Rep. Prog. Phys. 68 (2005) 1479. [28] M-H. Phan, S-C. Yu, J. Magn. Magn. Mater. 308 (2007) 325. [29] Kh. Sbissi. M. L. Kahn. M. Ellouze, F. Elhalouani, J Supercond Nov Magn. 28 (2015) 2899. [30] R. Cherif, E. K. Hlil, M. Ellouze, F. Elhalouani, S. Obbade, Journal of Solid State Chemistry 271 (2014) 215. [31] M. Mansouri, H. Omrani, W. Cheikhrouhou-Koubaa, M. Koubaa, A. Madouri, A. Cheikhrouhou, J. Magn. Magn. Mater. 401 (2016) 593. 12

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Tables Caption Table 1: Values of lattice parameter, unit cell volume (V), Mn–O–Mn bond angle, Mn–O bond length, profile factor (Rp), tolerance factor (t), weighted profile factor (Rwp), global chisquare (χ2), Bragg factor (RBragg) and crystallographic factor (RF) for Pr0.67Ba0.22Sr0.11Mn1xFexO3

manganites with x=0, 0.05,0.1 and 0.15.

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Table 2: Magnetic parameters for Pr0.67Ba0.22Sr0.11Mn1-xFexO3 (0 ≤ x ≤ 0.15) manganites.

  Table 3: Summary of |∆ |, the Curie temperature, RCP, ∆  and ∆  values for

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Pr0.67Ba0.22Sr0.11Mn1-xFexO3 (0 ≤ x ≤ 0.15) and for some magnetocaloric materials.

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x=0

x=0.05

x=0.10

x=0.15

symmetry

orthorhombic

orthorhombic

orthorhombic

orthorhombic

space group

Pnma

Pnma

Pnma

Pnma

a (Å)

5.5178(2)

5.5191(1)

5.5188(3)

5.5190(2)

b(Å)

7.7434(4)

7.7455(3)

7.7462(3)

7.7477(3)

⁄√ (Å)

5.4754(1)

5.476(4)

5.477(3)

5.4784(2)

c (Å)

5.4824(3)

5.4839 (2)

5.4836(3)

5.4851(2)

V (Å )

234.243

234.425

234.429

234.540

˂dMn–O˃(Å)

2.056(5)

2.028(5)

2.004(5)

2.002(5)

˂Mn–O–Mn˃(°)

165.750(1)

165.150(3)

166.400(4)

167.150(3)

t

0.9168

0.9168

0.9168

0.9168

˂rA>(Å)

1.2574

1.2574

1.2574

1.2574

Rp

7.57

7.54

7.35

7.38

Rwp

9.57

9.44

9.28

9.25

Rexp

8.05

7.69

7.85

8.10

Brag R-Factor

3.76

4.13

3.85

4.28

RF-Factor

8.57

7.73

7.13

8.24



1.41

1.51

1.3

1.63

DSC

88.67

94.05

94.29

93.27

70.79

69.45

71.14

70.05

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DWH

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parameters

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TC (K)

Θp (K)

μ (μ )

μ  (μ )

R-square

x=0

216

224.861(4)

7.12(5)

5.44

0.998

x=0.05

134

170.978(5)

7.51(5)

x=0.10

74

96.576(7)

7.75(4)

x=0.15

56

47.040(5)

7.93(5)

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Materials

0.987

5.54

0.993

5.59

0.983

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5.49

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µ0H

 ∆

RCP

∆ 

∆ 

(K)

(T)

(JK-1kg-1)

(Jkg-1)

(JK-1kg-1)

(JK-1kg-1)

Pr0.67Ba0.22Sr0.11MnO3

216

5

4.72

218

9.578

0.525

Our work

Pr0.67Ba0.22Sr0.11Mn0.95Fe0.05O3

134

5

1.90

175

4.33

-3.467

Our work

Pr0.67Ba0.22Sr0.11Mn0.9Fe0.10O3

74

5

1.45

122

3.754

-3.391

Our work

Pr0.67Ba0.22Sr0.11Mn0.85Fe0.15O3

56

5

0.83

79

0.622

-0.557

Our work

La0.67Ba0.22Sr0.11MnO3

303

5

4.85

290

-

-

[10]

La0.67Ba0.22Sr0.11 Mn0.9Fe0.10O3

270

5

3.24

155

-

-

[10]

Pa0.8 Bi0.2 Mn0.9Fe0.10O3

97

5

-

-

[29]

La0.6Pr0.1 Ba0.3 Mn0.9Fe0.10O3

277

5

La0.6Pr0.1 Sr0.3 Mn0.9Fe0.10O3

205

5

Pr 0.6Sr0.4Mn0.9Fe0.10O3

123

5

Gd

294

5

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Ref

2.12

106

3.24

155

[20]

2.33

198

[30]

3.66

223.52

[19]

10.2

410

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Materials

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[28]

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Figures caption Fig.1: Observed and calculated X-ray diffraction data and Rietveld refinement for Pr0.67Ba0.22Sr0.11Mn1-xFexO3 for x=0 (a) and x=0.05 (b). Vertical bars are the Bragg reflections

for the space group Pnma. The difference pattern between the observed data and fits is shown

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at the bottom. Fig. 2: Williamson-Hall analysis plots of Pr0.67Ba0.22Sr0.11Mn1-xFexO3 for x=0 (a) and x=0.05(b). Fig. 3: M (T) curves for Pr0.67Ba0.22Sr0.11Mn1-xFexO3 at µ0H = 0.05 T magnetic field in FC regime. The inset is the dM/dT curves.

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Fig. 4: Variation of the inverse of magnetic susceptibility versus temperature

Curie–Weiss law.

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Pr0.67Ba0.22Sr0.11Mn1-xFexO3 for x=0 (a) and x=0.05 (b). The green lines are the Fits according to

Fig. 5: Isothermal magnetization for Pr0.67Ba0.22Sr0.11Mn1-xFexO3 for x=0 (a) and x=0.05 (b) measured at several temperatures.

Fig. 6: H/M vs. M2 curves of isotherms for Pr0.67Ba0.22Sr0.11Mn1-xFexO3 for x=0 (a) and x=0.05

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(b).

Fig. 7: (a) and (b) Temperature dependence of the magnetic entropy change |∆‫ | ۻ܁‬for x=0 and x=0.05 at different applied magnetic field.

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Fig. 8: Specific heat change for for Pr0.67Ba0.22Sr0.11Mn1-xFexO3 for x=0 (a) and x=0.05 (b).

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