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Review on Magnetocaloric Effect and Materials

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DOI: 10.1007/s10948-018-4666-z

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Journal of Superconductivity and Novel Magnetism
https://doi.org/10.1007/s10948-018-4666-z

REVIEW PAPER

Review on Magnetocaloric Effect and Materials

N. Raghu Ram1 · M. Prakash1 · U. Naresh1 · N. Suresh Kumar2 · T. Sofi Sarmash1 · T. Subbarao1 · R. Jeevan Kumar1 ·
G. Ranjith Kumar4,5 · K. Chandra Babu Naidu3

Received: 17 February 2018 / Accepted: 24 March 2018

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Abstract
A detailed discussion of magnetocaloric properties of distinct materials is a vital aspect in magnetic refrigeration technology.
This review paper deals with all kinds of magnetocaloric materials such as ferromagnetic perovskites, glass ceramics, oxide-
based composites and spinel ferrites. The comparative study of magnetocaloric properties revealed that manganites have the
potential applications in magnetorefrigeration technology.

Keywords Ferromagnetic perovskites · Magnetocaloric effect · Entropy

1 Introduction harmful gasses and cooling efficiency is different. MCE

reduces the release of an amount of harmful gasses such
Magnetocaloric effect plays a major role in magnetic as chlorofluorocarbons (CFCs) and hydrofluoric carbons
refrigeration technology or heat pump application [1]. (HFCs) up to some extent rather than CGC. Therefore, the
The first magnetic device working at room temperature depletion of ozone is minimized that protects the health
is not developed till the middle of 1970s. However, the of the environment. In respect of cooling efficiency, MCE
magnetocaloric effect (MCE) is discovered before 1917. shows 20–50% more than CGC [4].
The MCE is discovered by French and Swiss physicists Recently, a number of materials are evolved in exhibiting
Weiss and Piccard, respectively [2]. MEC is a characteristic a MCE from different families such as perovskite mangan-
of magnetic material. When a magnetic field is applied ites, manganite alloys, glass ceramics and spinel ferrites.
to the specimen, it causes a change in magnetic state as Phan and Yu [4] reported rare-earth-doped manganites with
well as structural rearrangement which, in turn, produces a general formula R1−x Mx MnO3 (R = La, Nd, Pr and M =
a change of magnetic entropy (Sm ) [3]. Nowadays, Ca, Sr, Ba) for MCE applications. Also shown are various
MCE has emerged as a more advantageous technique applications such as heat pumps, large-scale air condi-
than conventional gas compression (CGC). However, these tioners, supermarket refrigeration liquor distilling, waste
are used for cooling applications; nevertheless, releasing separation, chemical processing, gas liquefaction and grain
drying. Barman and Kaur [5] improved MCE by magnetron
sputtering, achieving S = 15.2 mJ/cm3 /K at 272 K from
an isothermal M-H curve. Mo et al. [6] showed the highest
 K. Chandra Babu Naidu
[email protected] value of reversible change of entropy of −S = 40.4 J/kg/K
in case of EuTiO3 . Few oxide-based composites such as
1 Department of Physics, Sri Krishnadevaraya University, GdCrO4 -ErCrO4 , (0.95)La0.7 Sr0.3 MnO3 /Ni1−x Znx Fe2 O4
Anantapur, Andhra Pradesh, India and La0.8 Sr0.2 MnO3 /La0.8 K0.2 MnO3 [7–9] also exhibited
2 Department of Physics, JNTUA, Anantapur, Andhra Pradesh, prominent improvement of entropy change. Li et al.
India [10] reported an improved MEC effect of glass ceramics
3 Srinivasa Ramanujan Institute of Technology, Anantapur, (Fe-Tm-B-Nb) when compared with the existed litera-
Andhra Pradesh, India ture data. NiZnFe2 O4 , MnZnFe2 O4 and NiZnCuFe2 O4 ,
4 Department of Applied Sciences, REVA University, from spinel family [11–15], exhibited a magnetocaloric
Bangalore, India effect with varying fields. This article reviews the com-
5 Department of Physics, Rayalaseema University, Kurnool, parative entropy change with respect to the applied field
Andhra Pradesh, India variation.
 J Supercond Nov Magn

2 Theory of MCE

The MCE is generally referred as the isothermal change of

S (T1, H 1)
entropy (S) and adiabatic change of temperature (T )
upon the variation of magnetic field (H ). The value of
T is directly measured using a thermometer or indirectly

Entropy (S)
from specific heat data while S is calculated from
magnetization or specific heat. It is noted that entropy
change is governed by the following relation for materials S1
having a second-order phase transition:
S (T2, H 2)
 S
S = (∂M/∂T )dH (1)
T
According to the Launde theory, the second-order phase S2
transitions occur particularly in case of ferromagnetic
1 2
materials at TC (Curie point).
Temperature (T)
It is a well-known fact that total entropy (S) and magnetic
entropy (Sm ) are the important characteristics of a magnetic Fig. 1 S-T diagram at two varying fields of H1 and H2 for second-
material. Usually, S can be expressed in terms of magnetic order transition
field, temperature at a constant pressure and mathematically
given by [29]
S(H, T ) = Sm (H, T ) + Sl (H, T ) + Se (H, T ) (2) change in entropy (S = S2 − S1 ) and the adiabatic change
of temperature (T = T2 − T1 ) can be written as follows:
where Sl and Se are the lattice and electron contributions
to the resultant entropy and depend on applied field and S(T , H2 − H1 ) = S2 (T , H2 ) − S1 (T , H1 ) (5)
temperature. The nuclear contributions are avoided as
MCE is needed only at lower temperatures. The field and T (T , H2 − H1 ) = T2 (H2 ) − T1 (H1 ) (6)
temperature dependence of parameters in Eq. (2) cannot be
distinguished perfectly, since the electronic heat capacity As discussed by de Oliveira and von Ranke [16], Eqs. (5)
coefficient (ae ) is changed due the influence of external and (6) are identical to the following equations:
 H2
field at low temperatures. This, in turn, results in changing ∂S(T , H )
the magnetic structure and phase transition. Therefore, Sl S(T , H2 −H1 ) = S(T , H ) = dH (7)
H1 ∂H
and Se contributions depend on temperature while the rest of
the contributions depend on magnetic field. Thus, the lattice
energy can be expressed by the Debye interpolation formula

Sl = NR − 3ln(1 − exp(−Td /T ))
 Td /T  S (T, H 1)
x 3 dx
+12(T /Td )3 (3)
0 ex − 1
Entropy (S)

where N is the number of atoms per molecules, Td is the

Debye temperature and R is the ideal gas constant. Like-
wise, the electron entropy is obtained from the electronic
heat capacity (ae ) as follows:
S (T, H 2)
Se = ae T (4) S

Thus, the total entropy is calculated by substituting Eqs. T

(3) and (4) in Eq. (2). In general, for an applied field, the
total entropy of the system increases with temperature. On (H1)
P P
(H2)
ch
the other hand, entropy is decreasing with temperature. In
Fig. 1, it is shown that the variation of total entropy with Temperature (T)
increasing temperature for applied initial and final field Fig. 2 S-T diagram at two varying fields of H1 and H2 for first-order
limits H1 and H2 . For a condition H2 > H1 , the isothermal transition
J Supercond Nov Magn

Table 1 Magnetic entropy change (S), Curie point (TC ), field change (H ) and relative cooling power (RCP) parameters for manganites

Composition TC (K) MCE (H (T)) −S (J/kg/K) T (K) RCP (J/kg) Ref.

EuTiO3 5.7 5 40.4 8.1 328 [6]

Yb0.9 Er0.1 MnO3 3.7 2 0.5 0.7 1.7 [18]
– 4 0.9 1.7 6 [18]
– 6 1.5 3.4 13.8 [18]
– 8 2 5.4 23.1 [18]
Yb0.8 Er0.2 MnO3 3.7 2 0.5 0.7 1.5 [18]
– 4 1 1.8 6 [18]
– 6 1.6 3.5 13.9 [18]
– 8 2.1 5.6 23.8 [18]
GdCrO4 22 1 22.8 – – [7]
ErCrO4 14.9 1 20.5 – – [7]
GdCrO4 -ErCrO4 20 1 19.5 – 117 [7]
La0.7 (Ba, Sr)0.3 MnO3 316 2 1.27 – 75.7 [23]
La0.7 (Ba, Sr)0.3 Mn0.9 Ga0.1 O3 301 2 1.16 – 72.4 [23]
La0.7 (Ba, Sr)0.3 Mn0.8 Ga0.2 O3 300 2 1.02 – 71.3 [23]
Sm0.55 Sr0.45 MnO3 95 5 6.56 – 222.8 [25]
Sm0.45 Pr0.1 Sr0.45 MnO3 132 5 7.14 – 258.8 [25]
HoMnO3 75 7 8 5 540 [27]
La0.8 Ca0.2 MnO3 247 5 4.25 – 164 [30]
La0.8 K0.2 MnO3 281 5 3.71 – 160 [30]
La0.7 (Sr, Ba)0.3 MnO3 322 5 2.75 103.8 285.8 [31]
Pr0.6 Ca0.1 Sr0.3 Mn0.975 Fe0.025 O3 262 5 3.27 89.57 293 [32]
La0.6 Ca0.4 MnO3 260 0.5 0.3 120.2 37.4 [33]
La0.6 Ca0.4 MnO3 260 1 0.6 126.4 76.6 [33]
La0.6 Sr0.4 MnO3 370 0.5 0.23 120.8 27.4 [33]
La0.6 Sr0.4 MnO3 370 1 0.41 128.9 52.9 [33]
La0.6 Ca0.35 Sr0.05 MnO3 290 0.5 0.81 38.2 31.1 [33]
La0.6 Ca0.35 Sr0.05 MnO3 290 1 1.22 42.1 51.3 [33]
La0.5 Sr0.5 MnO3 340 3 0.63 – – [34]
NdMnO3 82 1 0.0037 – 0.025 [39]
La0.5 Ca0.5 Mn0.9 V0.1 O3 263 5 2.42 67.3 162.8 [41]
La0.5 Ca0.5 Mn0.95 V0.05 O3 230 5 3.12 70.9 221.3 [41]
SmFe0.5 Mn0.5 O3 234 7 5.6 – – [42]
La2/3 Ba1/3 Mn0.975 Fe0.025 O3 250 2.5 1.46 – – [43]
La1.1 Bi0.3 Sr1.6 Mn2 O7 340 5 1.65 81.5 134.4 [44]
Pr0.5 K0.05 Sr0.45 MnO3 310 5 1.66 164.2 272.5 [46]
Pr0.5 Na0.05 Sr0.45 MnO3 270 5 1.60 166.4 266.2 [46]
La1.2 Sr1.8 Mn2 O7 85 5 3.25 69.2 225 [47]
La0.7 Sr0.25 Bi0.05 MnO3 342 1 0.94 48 44 [49]
La0.7 Sr0.2 Bi0.1 MnO3 314 1 0.91 – – [49]
La0.7 Sr0.15 Bi0.15 MnO3 266 1 0.59 – – [49]
La0.7 Sr0.1 Bi0.2 MnO3 195 1 0.51 – – [49]
La0.7 Sr0.05 Bi0.25 MnO3 115 1 0.47 – – [49]
La0.7 Sr0.3 MnAlO3 367 0.01 0.162 2.4 0.388 [51]
La0.7 Sr0.28 MnAl0.02 O3 351 0.01 0.08 4.5 0.367 [51]
La0.7 Sr0.25 MnAl0.05 O3 335 0.01 0.04 8.6 0.343 [51]
La0.7 Sr0.2 MnAl0.10 O3 313 0.01 0.023 13.9 0.316 [51]
La0.7 Sr0.15 MnAl0.15 O3 278 0.01 0.013 25.3 0.321 [51]
 J Supercond Nov Magn

Table 1 (continued)

Composition TC (K) MCE (H (T)) −S (J/kg/K) T (K) RCP (J/kg) Ref.

La0.7 Sr0.10 MnAl0.20 O3 227 0.01 0.009 39.1 0.352 [51]

Pr0.8 Na0.2 K0 MnO3 92 5 3.2 111.1 355.6 [52]
Pr0.8 Na0.15 K0.05 MnO3 117 5 3.44 94.7 325.9 [52]
Pr0.8 Na0.1 K0.1 MnO3 125 5 3.32 88.0 292.2 [52]
Pr0.8 Na0.05 K0.15 MnO3 132 5 3.30 88.8 293.2 [52]
EuTi0.98 Cr0.02 O3 – 2 40 3 120 [54]
EuTi0.96 Cr0.04 O3 – 2 36.2 3.4 124 [54]
EuTi0.9 Cr0.1 O3 – 2 30 4.2 125 [54]
La0.67 Pb0.33 MnO3 358 4.8 4.43 – – [55]
(La0.9 Sm0.1 )0.67 Pb0.33 MnO3 341 4.8 4.31 – – [55]
(La0.8 Sm0.2 )0.67 Pb0.33 MnO3 311 4.8 4.35 – – [55]
(La0.7 Sm0.3 )0.67 Pb0.33 MnO3 286 4.8 3.64 – – [55]
La0.7 Sr0.3 MnO3 364 0.1 0.16 2.39 0.39 [63]
La0.7 Sr0.3 Mn0.25 Ti0.05 O3 307 0.1 0.42 3.02 0.19 [63]
La0.7 Sr0.3 Mn0.2 Ti0.1 O3 236 0.1 0.71 4.59 0.32 [63]
La0.6 Ca0.4 MnO3 270 5 8.3 61.2 508 [66]
La0.845 Sr0.155 MnO3 237 7 6.6 60 396 [67]

T (T , H2 −H1 ) = T (T , H ) where CH b and C a are the heat capacities of phases

 H2   H
∂S(T , H ) stable below and above Tp (magnetic transition point),
=− [T /C (T , H )] dH respectively. It is considered that at a constant field, all these
H1 ∂H
(8) are equal to CH (T ). Therefore, the total entropy change for
where C(T , H ) = C(T , H ) + Cl + Ce is the heat capacity the conditions T < Tp , Tp (H1 ) < T < Tp (H2 ) and T > Tp ,
and C(T , H ), Cl and Ce are the magnetic, lattice and respectively, can be written as follows:
electron contributions of heat capacity, respectively.
 T CH (T , H 2) − CH (T , H 1)
C(T , H ) = T (∂Sm (T , H )/∂T )H (9) S(T , H ) = dT (13)
0 T
Using the Maxwell equation (∂Sm (T , H )/∂H )T = (∂M
(T , H )/∂T )H , Eqs. (7) and (8) can be replaced as follows:
 H2 
∂M(T , H ) CH (T , H 2) − CH (T , H 1)
T
S(T , H ) = dH (10) S(T , H ) = dT
H1 ∂T 0 T
E(H 1)
Equation (10) helps us to find the isothermal magne- − (14)
Tp (H 1)
tocaloric potential (S) for the second-order transition
using magnetization vs. temperature (M-T ) curves.
 H2   
∂M(T , H ) CH (T , H 2) − CH (T , H 1)
T
T (T , H ) = − [T /C (T , H )] dH S(T , H ) = dT
H1 ∂T 0 T
(11) E(H 1) E(H 2)
− + (15)
Tp (H 1) Tp (H 2)
For the first-order (FO) phase transition, schematic graph
is shown in Fig. 2.
Tch is the characteristic temperature of transition point where E(H )
Tp (H ) is a temperature-independent value, and
temperatures (Tp ) at H1 and H2 fields. The FO phase likewise, the adiabatic change of temperature can be given
transition equation can be written as by
 TP (H ) b  T a (T , H )
CH (T , H ) CH T
S(T , H ) = dT + dT T (T , H ) = S(T , H )
0 T Tp (H ) T CH (H, T )
E(H ) T E(H 1)
+ (12) = (16)
Tp (H ) CH (H, T ) Tp (H 1)
J Supercond Nov Magn

Table 2 Magnetic caloric parameters of amorphous-based composites and alloyed materials

Composition TC (K) MCE (H (T)) S (J/kg/K) T (K) RCP (J/kg) Ref.

Ni50.3 Mn36.9 Sb12.8 365 2 9.4 – 85 [5]

Ni50.2 Mn36.7 Sb11.9 Al1.2 345 2 11.8 – 126 [5]
Ni50 Mn36.3 Sb10.4 Al3.3 331 2 15.2 – 135 [5]
Ni49.7 Mn36.4 Sb8.3 Al5.6 324 2 – – – [5]
Ni47.74 Mn37.06 In15.20 282 5 30.7 30 – [19]
Fe60 Ru20 B20 255 2 −0.80 – 140 [20]
255 5 −1.52 – 394 [20]
(Fe0.76 B0.24 )96 Nb4 559 1.5 1.51 – 121 [10]
(Fe0.75 Tm0.01 B0.24 )96 Nb4 537 1.5 1.39 – 108 [10]
(Fe0.71 Tm0.05 B0.24 )96 Nb4 450 1.5 1.21 – 91 [10]
(Fe0.66 Tm0.10 B0.24 )96 Nb4 390 1.5 1.00 – 76 [10]
(Fe0.59 Tm0.17 B0.24 )96 Nb4 316 1.5 0.91 – 59 [10]
(Fe0.58 Tm0.18 B0.24 )96 Nb4 325 1.5 0.87 – 57 [10]
LaFe11.4 Si1.6 H0.21 235 5 15 – 352 [21]
LaFe11.4 Si1.6 H0.41 267 5 15.1 – 317 [21]
LaFe11.4 Si1.6 H0.86 282 5 16.5 – 274 [21]
Mn3 GaC 245 1 −1.4 – 21.8 [22]
Mn3 Ga0.9 Ge0.1 C 235 1 −1.3 – 20.1 [22]
Mn3 Ga0.8 Ge0.2 C 220 1 −1.2 – 19.5 [22]
DyPtGa – 5 6.5 4.1 131.2 [24]
HoPtGa – 5 9.2 4.7 176.6 [24]
EuPtGa – 5 8.1 6.7 158.8 [24]
ErNiBC 5 5 24.8 8.6 312 [26]
CoMn0:9 Fe0:1 Ge 290 5 −34.9 8.5 240 [28]
GdNiAl2 28 5 16 40 640 [35]
Fe72 V8 B12 Si8 474 0.5 −3 – – [36]
Fe70 V10 B12 Si8 436 0.5 −2.4 – – [36]
Fe66.3 V13.7 B12 Si8 335 0.5 −1.6 – – [36]
Gd2 In 188 4 −4.5 – – [37]
Gd2 In0.8 Al0.2 190 4 −5.0 – – [37]
Gd2 In0.8 Pb0.2 243 4 −3.3 – – [37]
Ni48 Mn39.5 Sn10.5 Al2 301 5 7.9 21 165.9 [40]
Ni50 Co2 Mn33 In15 298 5 21.5 19.1 410 [45]
(MnCoGe)0.89 (NiCoGe)0.11 300 5 −24.1 10.7 257.4 [48]
MnCoGe)0.88 (NiCoGe)0.12 270 5 −23.5 9.6 224.3 [48]
MnCoGe)0.87 (NiCoGe)0.13 240 5 −20.4 8.7 176.6 [48]
(Fe0.71 Tb0.05 B0.24 )96 Nb4 448 1.5 1.08 – – [50]
(Fe0.71 Ho0.05 B0.24 )96 Nb4 440 1.5 1.11 – – [50]
(Fe0.71 Tm0.05 B0.24 )96 Nb4 453 1.5 1.21 – – [50]
Mn1.15 Fe0.85 P0.52 Si0.45 B0.03 251 2 −19.8 10.5 207.9 [53]
MnCoGe0.995 In0.005 (1 GPa) 320 5 30 10 300 [56]
MnCoGe0.995 In0.005 (3 GPa) 310 5 65 54 351 [56]
MnCoGe0.995 In0.005 (5 GPa) 306 5 3.2 73 235 [56]
Mn39 Co26 Ge35 300 0.05 1.76 4 7.04 [57]
Dy3 Al2 94 5 12.1 29.7 360 [58]
Mn1.1 Fe0.9 P0.87 Ge0.13 248 5 9.6 13.4 129 [59]
Mn1.1 Fe0.9 P0.81 Ge0.19 255 5 27.5 17.5 482 [59]
Mn1.1 Fe0.9 P0.79 Ge0.21 281.5 5 26.4 43.1 1138 [59]
 J Supercond Nov Magn

Table 2 (continued)
Composition TC (K) MCE (H (T)) S (J/kg/K) T (K) RCP (J/kg) Ref.

Mn1.1 Fe0.9 P0.74 Ge0.26 345 5 18.2 26.5 483 [59]

Mn1.1 Fe0.9 P0.68 Ge0.32 401.7 5 9.5 63 598.5 [59]
Ni48.4 Co34.2 Mn34.2 In13.8 Ga1.7 295 5 5.7 50 285 [60]
Gd55 Co25 Al20 (ribbon) 110 5 10.1 70.8 715 [61]
TmZnAl 2.8 7 11.8 24.5 289 [62]
TmAgAl 3.2 7 14.1 22.3 315 [62]
Gd (bulk) 293 5 9.4 73.4 690 [65]
Ni43 Mn46 Sn8 In3 260 3 7.2 23.9 172 [67]

3 Magnetocaloric Materials ions [4]. Magnetic entropy change (S), Curie point (TC ),
field change (H ) and relative cooling power (RCP)
3.1 Perovskites are regarded as the variable parameters of magnetocaloric
effect. The comparative studies on the results of MCE of
Perovskites are of usually cubic structures having a general manganites, glass composites, alloys and spinel ferrites are
formula of ABO3 . In this structure, A site may be commonly given in Tables 1, 2 and 3, respectively.
occupied by rare-earth or alkaline-earth element while B Rare-earth-based manganites are considered as best
site is occupied by a transition metal ion. Few perovskite materials for MEC in refrigeration technology. However,
materials show change structure at room temperature. This extensive studies are made on AMnO3 (A = La, Pr, Sr,
happens owing to the instability of structure. The stability Ba and Ca)-like structures [23]. Recently, a number of
of perovskites is governed by tolerance factor (t). It can new manganites have emerged, exhibiting advanced RCP.
be mathematically
√ represented by a standard relation: t = RCP is a measure of the amount of heat transferred by a
RA + RB / 2 (RB + RO ), where RA , RB and RO are refrigerant per ideal cycle and is usually obtained from the
the ionic radii of A site, B site and oxygen (0.155 nm) product of negative maxima of isothermal entropy change
ions, respectively. The materials possessing a t value in the (−S) and full width at half maxima of temperature
range of 0.8–1.0 show a stable cubic perovskite structure change (T ) in −S against T plots of a given system, i.e.
while for lower values (t <0.8), the lattice site will fluctuate RCP = (−S × T ). This should be as high as possible in
[17]. Therefore, there is a possibility for changing the order to show better cooling efficiency. In Fig. 3, the evalu-
structure. For instance, MnO6 exhibits two structures, say ation of RCP is evidently shown for La0.7 Ca0.25 Sr0.05 MnO3
orthorhombic and rhombohedral, due to lattice fluctuations, single crystal, since long-time gadolinium (Gd) is an
since manganese performs multiple valencies and, for each effective material at room temperature (RT) for RCP
valency, the t value is changed. Thus, for t < 0.96, MnO6 applications. Phan and Yu [4] reviewed the RCP of
attributes an orthorhombic structure. On the other hand, for various manganites and summarized that few composi-
0.96 < t < 1, it attains a rhombohedral structure. This, tions such as La0.845 Sr0.155 MnO3 , La0.815 Sr0.185 MnO3 ,
in turn, alters the bond angle between B site and oxygen La0.7 Ca0.25 Sr0.05 MnO3 , Gd5 Si2 Ge2 and Pr0.63 Sr0.37 MnO3

Table 3 Magnetocaloric
parameters of spinel ferrites Composition TC (K) MCE (H (T)) S (J/kg/K) T (K) RCP (J/kg) Ref.

Zn0.6 Cu0.4 Fe2 O4 305 5 1.16 – 289 [15]

Zn0.4 Ni0.2 Cu0.4 Fe2 O4 565 5 1.41 – 141 [15]
Zn0.2 Ni0.4 Cu0.4 Fe2 O4 705 5 1.61 – 233 [15]
Cu0.4 Zn0.6 Fe2 O4 373 3 1.27 – 36.7 [38]
Cu0.3 Zn0.7 Fe2 O4 272 3 0.91 – 36.5 [38]
Cu0.2 Zn0.8 Fe2 O4 143 3 0.77 – 37.8 [38]
Zn0.6 Ni0.4 Fe2 O4 460 1.7 0.025 – – [13]
NiFe0 O4 845 2.5 0.75 80 60 [64]
Ni0.7 Zn0.3 Fe2 O4 664 2.5 1.39 48.9 68 [64]
Ni0.5 Zn0.5 Fe2 O4 481 2.5 1.15 140 161 [64]
Ni0.3 Zn0.7 Fe2 O4 302 2.5 0.86 139.5 120 [64]
J Supercond Nov Magn

attributed highest RCP values of 670, 533, 462, 535 and 511 30
J/kg, respectively. In this review, some additional compo- Yb0.9Er0.1MnO3
25
sitions of HoMnO3 , La0.6 Ca0.4 MnO3 , Pr0.8 Na0.2 K0 MnO3 , 25 Yb0.8Er0.2MnO3

Pr0.8 Na0.15 K0.05 MnO3 , Pr0.8 Na0.1 K0.1 MnO3 and Pr0.8 Na0.05 20
K0.15 MnO3 have performed the RCP of 540, 508, 356, 20
326, 292 and 293 J/kg, respectively. The rest of manganites 15

RCP (J/kg)

RCP (J/kg)
attributed a moderate cooling power. As summarized in 15
Table 1, in case of Yb0.9 Er0.1 MnO3 and Yb0.8 Er0.2 MnO3 10
for an increasing value of H , the relative cooling power is 10
increasing. This confirmed the linear proportional relation 5
between them and is depicted in Fig. 4. 5

0
3.2 Glass Composites and Alloys 0
2 4 6 8
Glass composites have potential applications in mag- H (T)
netic refrigeration (MR) technology. The phase transitions
and critical behavior of composites can be suitable for Fig. 4 The variation of relative cooling power with H (field change)
of Yb0.9 Er0.1 MnO3 and Yb0.8 Er0.2 MnO3
finding the ferromagnetic nature [36]. In Table 2, mag-
netocaloric parameters are listed for distinct amorphous-
based ferromagnetic composites and alloys. Few mate- 3.3 Spinel Ferrites
rials such as Fe60 Ru20 B20 , LaFe11.4 Si1.6 H0.21 ,GdNiAl2 ,
Ni50 Co2 Mn33 In15 , Mn1.1 Fe0.9 P0.81 Ge0.19 , Mn1.1 Fe0.9 P0.79 Ferrites are of AB2 O4 spinel structures. For magnetic
Ge0.21 , Mn1.1 Fe0.9 P0.74 Ge0.26 , Ni48.4 Co34.2 Mn34.2 In13.8 Ga1.7 cooling technology, extensive investigations have not been
and Gd55 Co25 Al20 (ribbon) attributed an appreciable rela- done on spinels of AB2 O4 (A = Mn, Fe, Co, Ni, Cu
tive cooling power. The effect of pressure variation on RCP and Zn). However, few ferrite compositions including
is illustrated for MnCoGe0.995 In0.005 (1 GPa), MnCoGe0.995 MEC parameters are listed in Table 3. It is observed that
In0.005 (3 GPa) and MnCoGe0.995 In0.005 (5 GPa). The Zn0.6 Cu0.4 Fe2 O4 and Zn0.2 Ni0.4 Cu0.4 Fe2 O4 attributed RCP
increasing pressure increases the cooling power. In compar- values of 289 and 233 J/kg, respectively, at H = 5T .
ing these RCP values with manganite data, it is understood Therefore, these are useful for cooling power technology.
that alloyed materials have performed a high cooling power
than the manganites.
4 Conclusions

12 Magnetocaloric materials provide better cooling and envi-

- Smax ronment protection from various gasses. Moreover, room-
10 La0.7Ca0.25Sr0.05MnO3 temperature relative cooling is being used throughout the
world. It is believed that alloyed materials have performed
RCP = - Smaxx Tfwhm superior magnetocaloric properties than the manganites.
8
- S (J/kgK)

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