Journal of Magnetism and Magnetic Materials 456 (2018) 236–240

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Journal of Magnetism and Magnetic Materials

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Research articles

Magnetic properties and large reversible magnetocaloric effect in Er3Pd2

Bibekananda Maji a,⇑, Mayukh K. Ray b, M. Modak b, S. Mondal b,c, K.G. Suresh d, S. Banerjee b
a
Acharya Jagadish Chandra Bose College, 1/1B, A. J. C. Bose Road, Kolkata 700020, India
b
Saha Institute of Nuclear Physics, HBNI, 1/AF Bidhannagar, Kolkata 700064, India
c
Department of Physics, Visva–Bharati, Santiniketan 731 235, India
d
Department of Physics, Indian Institute of Technology Bombay, Mumbai 400076, India

a r t i c l e i n f o a b s t r a c t

Article history: The magnetic properties and magnetocaloric effect (MCE) of binary intermetallic compound Er3Pd2 were
Received 16 October 2017 studied. It exhibits a paramagnetic (PM) to antiferromagnetic (AFM) transition at Néel temperature (TN)
Received in revised form 2 January 2018 = 10 K. A large reversible MCE was observed which is related to a second order magnetic transition from
Accepted 12 February 2018
PM to AFM state. The values of maximum magnetic entropy change ðDSmax M Þ and adiabatic temperature
Available online 13 February 2018
change ðDT max
ad Þ reach 8.9 J/kg-K and 2.9 K respectively for the field change of 50 kOe with no obvious hys-
teresis loss. The effective magnetic moment was determined to be 10.16 mB/Er3+, which is notably higher
Keywords:
than that of free ion value of Er3+ (9.59 mB), suggests that Pd ions also have considerable amount of mag-
Intermetallic
Rare earth
netic moments in this compound.
Reversible magnetocaloric effect Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction applications, it is of great importance to realize large MCE over a

wide temperature region. In contrast to the FOMT, comparatively
The quest for realizing a cooling method alternative to conven- low but highly reversible MCE observed in materials with second
tional vapor compression based refrigeration technology has given order magnetic transitions (SOMT). Also, owing to broad magnetic
birth to magnetic refrigeration, which is based on the phenomenon transition, the temperature range of MCE is usually large in SOMT.
called magnetocaloric effect (MCE). Magnetic refrigeration is an Therefore, it is necessary to search for magnetic materials with
environmental friendly solid state cooling technology which uses optimal magnetocaloric properties i.e., large reversible MCE
magnetic field to cool the magnetic refrigerant materials. The together with large RCP values over a wide temperature region
isothermal magnetic entropy change (DSM) and an adiabatic tem- associated with a SOMT.
perature change (DTad), when the material is exposed to a mag- In order to search for active refrigerant materials, rare-earth
netic field are used to measure and represent MCE. Apart from based compounds have been extensively studied in recent past
the large values of DSM and DTad, the large relative cooling power and some of them have emerged as potential refrigerant materials
(RCP) is considered to be other important qualities of refrigerant [7–21]. Notably, table shaped MCE, where DSM remains almost
materials. In this respect, materials having first order magnetic unchanged over a wide temperature span, has been reported in
transition (FOMT) are extensively studied since the discovery of various materials with multiple successive phase transitions and
giant MCE in Gd5Si4-xGex, LaFe13-xSixH and MnFeP (As, Ge) [1–6]. also in some composite materials [22–27]. Such materials are of
However, the practical application of such materials has been con- the utmost importance because of their huge RCP even though
fined by the first order nature of the transition itself, since the first the DSM is not so large in some cases.
order transition is usually accompanied by thermal and magnetic The binary intermetallic compound Er3Pd2, which crystallizes in
hysteresis losses and hence leads to the irreversibility in DSM the U3Si2 – type tetragonal structure with the space group P4/
and DTad curves. This can reduce the RCP of magnetic refrigerant mbm, seems to be particularly important since it exhibits a large
materials drastically. Also, the temperature span of the MCE is usu- reversible MCE associated with a SOMT at low temperature
ally very narrow in case of materials with FOMT. But, for practical (around 10 K). In this paper, we present the magnetic properties
and the magnetocaloric effect of Er3Pd2 compound by magnetiza-
tion and heat capacity measurements. Although this binary phase
⇑ Corresponding author. was known for a long time, a very little about structural and mag-
E-mail address: bibekanandamaji@gmail.com (B. Maji). netic properties were studied before.

https://doi.org/10.1016/j.jmmm.2018.02.036
0304-8853/Ó 2018 Elsevier B.V. All rights reserved.
 B. Maji et al. / Journal of Magnetism and Magnetic Materials 456 (2018) 236–240 237

2. Experimental details

Polycrystalline sample of Er3Pd2 was prepared by arc melting

stoichiometric mixture of the constituent elements of Er (99.9-at.
% purity) and Pd (99.99-at.% purity) in a water-cooled copper
hearth, in high purity argon atmosphere. The resulting ingot was
turned upside down and remelted five times to ensure homogene-
ity. The weight loss after the final melting was less than 0.5%. The
arc melted button was sealed in an evacuated quartz tube and
annealed at 800 °C for 1 week. The structural analysis of the
annealed sample was performed by collecting the room tempera-
ture powder X-ray diffractogram (XRD) using Cu-Ka radiation.
The temperature and field dependence of the magnetization were
measured using vibrating sample magnetometer (VSM) option in
physical property measurement system (PPMS, Quantum Design).
The heat capacity measurements were carried out by adiabatic
heat relaxation method using the PPMS.
Fig. 2. Temperature dependence of ZFC and FC magnetizations for Er3Pd2
3. Results and discussions compound at magnetic field of 500 Oe (left axis). Temperature variation of the
inverse dc susceptibility fitted to the Curie–Weiss law (right axis).

The Reitveld refinement of the room temperature XRD pattern

(shown in Fig. 1) was performed by using Full-prof program. It is negative sign of hp reveals that the magnetic interactions are anti-
evident that all main peaks can be indexed with U3Si2 type tetrag- ferromagnetic. Considering only Er3+ ions as paramagnetic ions at
onal structure of space group P4/mbm, except for few tiny peaks the higher temperature (paramagnetic region), the effective mag-
corresponding to unreacted Er and Pd phase. Such impurity phases netic moment (meff) has been determined to be 10.16 mB/Er3+ .The
might be reduced by optimizing the annealing process and stoi- evaluated value of meff is notably higher than that of free ion value
chiometry ratio of the starting materials. According to the refine- of Er3+ (9.59 mB). Such discrepancy of meff suggests that not just Er3+
ment analysis Er atoms seat in 2a and 4 h Wyckoff sites, where ions but Pd ions also contribute to the magnetic moment in this
as the 4 g sites are occupied by Pd atoms. The evaluated lattice compound. Therefore, the magnetic interactions and hence mag-
parameters are as follows: a = b = 7.6776(4) Å, c = 3.9082(2) Å netic properties arise due to both the rare earth as well as transi-
and a = b = c = 90°. tion metal ions in this compound.
Zero field cooled (ZFC) and field cooled (FC) magnetization A set of magnetic isotherms were measured within the temper-
curves of Er3Pd2 as a function of temperature at 500 Oe are shown ature range from 8 K to 50 K up to 50 kOe field. There is no visible
in Fig. 2. As clearly follows, a paramagnetic (PM) to antiferromag- hysteresis at any temperature particularly around TN. In order to
netic (AFM) transition is observed on cooling at TN = 10 K. There is understand the nature of the magnetic transition we have plotted
no obvious thermal hysteresis observed around TN which indicates M2 versus H/M which is known as Arrott Plots (Fig. 3(b)). Neither
that PM-AFM transition is of second order type. The inverse sus- the inflection point nor negative slopes are observed, indicating
ceptibility (v1) and the Curie–Weiss fit to the experimental data the occurrence of pure second order magnetic transition in Er3Pd2.
for Er3Pd2 compound are shown in the right hand side axis of The magnetic entropy change (DSM) was calculated from magneti-
Fig. 2. In the paramagnetic region, the inverse susceptibility fol- zation isotherms data using Maxwell’s relation [28]:
lows the Curie-Weiss law; v1 = (T  hp)/C, where hp is the param- RH  
DSM ðT; DHÞ ¼ Hif @MðT;HÞ
@T
dH. The temperature dependence of
agnetic Curie temperature and C is the Curie-Weiss constant. The H
paramagnetic Curie temperature hp is obtained to be 6 K. The DSM data for different magnetic field variations up to 50 kOe is

Fig. 1. (a) Rietveld fitted room temperature XRD pattern of Er3Pd2. Asterisks and arrows indicate the positions of the Er and Pd impurity phases respectively. (b) The unit cell
of Er3Pd2. 2a and 4 h Wyckoff sites are occupied by Er and 4 g are occupied by Pd atoms.
238 B. Maji et al. / Journal of Magnetism and Magnetic Materials 456 (2018) 236–240

Fig. 3. (a) Magnetization isotherm for Er3Pd2 at different temperatures. (b) Arrott plots (M2 vs. H/M plots) in the temperature range 8 K to 50 K.

shown in Fig. 4. The maximum value of DSM for a field change of 50 where H is the magnetic field under which the heat capacity was
kOe is 8.9 J/kg-K at 12 K. Although the maximum value of DSM is measured. The isothermal entropy change and adiabatic tempera-
smaller than those which undergoes FOMT, the present value is ture change can be calculated using the following formulas:
comparable with those having second order magnetic transitions
DSM ðT; DHÞ ¼ SðT; Hf Þ  SðT; Hi Þ ð2Þ
e.g. PrCo2B2, GdPd2Si, PrNi, (Ho, Tb, Dy)2In etc. [29–34].
The temperature dependency of heat capacity, Cp(T), of Er3Pd2
DT ad ðT; DHÞ ¼ TðS; Hf Þ  TðS; Hi Þ ð3Þ
sample was also measured in zero and 50 kOe magnetic field. As
shown in the left panel of Fig. 5, zero field Cp(T) curve exhibits a The temperature dependency of DSM and DTad estimated from
k- shape peak around 10 K indicating a typical SOMT correspond- the Eqs. (2) and (3) are shown in Fig. 5(a) and (b). For comparison,
ing to AFM to PM transition confirmed from the magnetic mea- we have also plotted (in the same figure) the temperature depen-
surements. The Néel temperature (TN) determined from the heat dency of DSM derived by using the magnetization isotherms and
capacity data is 9 K which is consistent with that deduce from Maxwell relation. As evident from the figure, the temperature vari-
the magnetization measurement. Using the field dependency of ation of DSM obtained from heat capacity data and magnetization
Cp(T) data, one can estimate the total entropy at different magnetic isotherm are almost the same over the measured temperature
field by the following integration: range. It can be also seen that the temperature dependency of
Z T   DSM and DTad are also almost similar except a slight difference
CðT; HÞ
SðT; HÞ ¼ dT ð1Þ in temperature of the peak position. The maximum value of mag-
T
0 H
netic entropy change ðDSmax M Þ and adiabatic temperature change
ðDT max
ad Þ reach 8.9 J/kg-K and 2.9 K respectively for a field change
of 50 kOe. As mentioned above, relative cooling power (RCP) is
another significant quality of the refrigerant materials which is
essentially the amount of heat transfer between the cold and hot
sinks in an ideal refrigeration cycle. The RCP is estimated as the
product of maximum magnetic entropy change ðDSmax M Þ and the
full width at half maximum in DSM ðTÞ curve i.e. RCP =
DSmax
M  dT FWHM . The dT FWHM value is 22.8 K for a field change of
50 kOe and the corresponding RCP value is 201 J/kg. The maximum
values of DSM ðTÞ, DTad and RCP for the field change 50 kOe and
the transition temperature (TM) for Er3Pd2 and some other MCE
materials with similar transition temperature are listed in Table 1.
The values of DSmax M and DT max
ad are comparable with some of the
MCE materials with similar temperature region.

4. Conclusion

From the magnetization and heat capacity measurements we

found that Er3Pd2 undergoes paramagnetic to antiferromagnetic
transition at 10 K on cooling and it exhibits large reversible MCE.
There is no thermal and magnetic hysteresis around the Néel tem-
perature. The maximum value of isothermal magnetic entropy
Fig. 4. Temperature dependence the magnetic entropy change for various magnetic change ðDSmax max
M Þ and adiabatic temperature change (DT ad Þ are
field changes up to 50 kOe. estimated to be 8.9 J/kg-K and 2.9 K respectively for a field change
 B. Maji et al. / Journal of Magnetism and Magnetic Materials 456 (2018) 236–240 239

Fig. 5. (a) Heat capacity, Cp of Er3Pd2 as a function of temperature at magnetic field 0 and 50 kOe. (b) Temperature variation of magnetic entropy change, DSM, obtained
from heat capacity (square symbols) and magnetization measurements (circular symbols) for a field change of DH = 50 kOe. (c) Adiabatic temperature change, DTad, for a field
change of DH = 50 kOe.

Table 1
The transition temperature (TM), the order of transition, the maximum values of magnetocaloric parameters (DSmax max
M , DT ad and RCP) for a field change of 50 kOe for Er3Pd2, and
some MCE materials. A blank column with ‘‘——” mark indicates that the value is not available in the literatures.

Materials T M ðKÞ Order of transition DSmax

M ðJ=Kg-KÞ DT max
ad ðKÞ
RCP (J/kg) Ref.

Er3Pd2 10 Second 8.9 2.9 201 Present work

PrCo2B2 16 Second 8.1 8.1 —— [29]
DyCo2B2 10 Second 12.2 —— —— [35]
ErRu2Si2 5.5 First 17.6 12.9 262 [7]
Dy0.9Tm0.1Ni2B2C 9.2 First 14.7 —— 279 [36]
PrNi 20 Second 6.1 1.7 —— [31]
GdPd2Si 17 Second 15.0 8.5 —— [30]
ErAgAl 14 Second 10.5 —— 261 [37]
Dy2CoGa3 17 Second 10.8 —— 252 [38]
TmZn 8 First 26.9 8.6 269 [13]
TmZnAl 2.8 Second 9.4 —— 189 [15]
TmAgAl 3.3 Second 12.4 —— 214 [15]
Dy2CuSi3 9.6 Second 13.2 —— 275 [17]
Tm4CoCd 4.5 Second 15.8 —— 345 [20]
HoNiAl2 7.8 Second 14.0 —— 213 [21]
TbCo3B2 28 Second 8.7 7.3 —— [39]

of 50 kOe. The reliability of the parameters can be justified from [8] L. Li, K. Nishimura, W.D. Hutchison, Z. Qian, D. Huo, T. Namiki, Appl. Phys. Lett.
100 (2012) 152403.
the observed overlapping of change in entropy ðDSmax M Þ curves [9] L. Li, W.D. Hutchison, D. Huo, T. Namiki, Z. Qian, K. Nishimura, Scripta Mater.
obtained from specific heat and magnetization data. 67 (2012) 237.
[10] S.B. Gupta, K.G. Suresh, Appl. Phys. Lett. 102 (2013) 022408.
[11] L. Li, B. Saensunon, W.D. Hutchison, D. Huo, K. Nishimura, J. Alloys Compd. 582
Appendix A. Supplementary data (2014) 670.
[12] B. Maji, M.K. Ray, K.G. Suresh, S. Banerjee, J. Appl. Phys. 116 (2014) 213913.
[13] L. Li, Y. Yuan, Y. Zhang, T. Namiki, K. Nishimura, R. Pöttgen, S. Zhou, Appl. Phys.
Supplementary data associated with this article can be found, in Lett. 107 (2015) 132401.
the online version, at https://doi.org/10.1016/j.jmmm.2018.02.036. [14] Ling-Wei Li, Chin. Phys. B 25 (2016) 037502.
[15] Y. Zhang, L. Hou, Z. Ren, X. Li, G. Wilde, J. Alloys Compd. 656 (2016) 635–639.
[16] Y. Yang, Y. Zhang, X. Xu, S. Geng, L. Hou, X. Li, Z. Ren, G. Wilde, J. Alloys Compd.
References 692 (2017) 665–669.
[17] Y. Zhang, D. Guo, Y. Yang, S. Geng, X. Li, Z. Ren, G. Wilde, J. Alloys Compd. 702
(2017) 546–550.
[1] V.K. Pecharsky, K.A. Gschneidner Jr., Phys Rev. Lett. 78 (1997) 4494.
[18] L. Li, G. Hu, Y. Qi, I. Umehara, Sci. Rep. 7 (2017) 42908.
[2] F.X. Hu, B.G. Shen, J.R. Sun, Z.H. Cheng, G.H. Rao, X.X. Zhang, Appl. Phys. Lett. 78
[19] Y. Zhang, D. Guo, H. Li, S. Geng, J. Wang, X. Li, H. Xu, Z. Ren, G. Wilde, J. Alloys
(2001) 3675.
Compd. 733 (2018) 40–44.
[3] A. Fujita, S. Fujieda, Y. Hasegawa, K. Fukamichi, Phys Rev. B 67 (2003) 104416.
[20] L. Li, D. Huo, K. Su, R. Pöttgen, Intermetallics 93 (2018) 343.
[4] J. Lyubina, K. Nenkov, L. Schultz, O. Gutfleisch, Phys Rev. Lett. 101 (2008)
[21] Y. Zhang, D. Guo, Y. Yang, J. Wang, S. Geng, X. Li, Z. Ren, G. Wilde, Intermetallics
177203.
88 (2017) 61–64.
[5] A. Yan, K.H. Müller, L. Schultz, O. Gutfleisch, J. Appl. Phys. 99 (2006) 08K903.
[22] A. Chaturvedi, S. Stefanoski, M.H. Phan, G.S. Nolas, H. Srikanth, Appl. Phys. Lett.
[6] O. Tegus, E. Brück, K.H.J. Buschow, F.R. de Boer, Nature 415 (2002) 150.
99 (2011) 162513.
[7] T. Samanta, I. Das, S. Banerjee, Appl. Phys. Lett. 91 (2007) 152506.
240 B. Maji et al. / Journal of Magnetism and Magnetic Materials 456 (2018) 236–240

[23] R. Caballero-Flores, V. Franco, A. Aonde, K.E. Knipling, M.A. Willard, Appl. Phys. [32] Q. Zhang, X.G. Liu, F. Yang, W.J. Feng, X.G. Zhao, D.J. Kang, Z.D. Zhang, J. Phys. D:
Lett. 98 (2011) 102505. Appl. Phys. 42 (2009) 055011.
[24] L. Li, M. Kadonaga, D. Huo, Z. Qian, T. Namiki, K. Nishimura, Appl. Phys. Lett. [33] Q. Zhang, J.H. Cho, J. Du, F. Yang, X.G. Liu, W.J. Feng, Y.J. Zhang, J. Li, Z.D. Zhang,
101 (2012) 122401. Solid State Commun. 149 (2009) 396.
[25] L. Li, T. Namiki, D. Huo, Z. Qian, K. Nishimura, Appl. Phys. Lett. 103 (2013) [34] Q. Zhang, J.H. Cho, B. Li, W.J. Hu, Z.D. Zhang, Appl. Phys. Lett. 94 (2009) 182501.
222405. [35] L. Li, K. Nishimura, G. Usui, D. Huo, Z. Qian, Intermetallics 23 (2012) 101.
[26] L. Li, O. Niehaus, M. Kersting, R. Pöttgen, Appl. Phys. Lett. 104 (2014) 092416. [36] L. Li, K. Nishimura, Appl. Phys. Lett. 95 (2009) 132505.
[27] L. Li, Y. Yuan, Y. Qi, Q. Wang, S. Zhou, Mater. Res. Lett. 6 (2017) 67–71. [37] Y. Zhang, B. Yang, G. Wilde, J. Alloys Compd. 619 (2015) 12.
[28] V.K. Pecharsky, K.A. Gschneidner Jr., J. Appl. Phys. 86 (1999) 565. [38] L.C. Wang, L. Cui, Q.Y. Dong, Z.J. Mo, Z.Y. Xu, F.X. Hu, J.R. Sun, B.G. Shen, J. Appl.
[29] L. Li, K. Nishimura, J. Appl. Phys. 106 (2009) 023903. Phys. 115 (2014) 233913.
[30] R. Rawat, I. Das, J. Phys.: Condens. Matter 13 (2001) L57. [39] L. Li, D. Huo, H. Igawa, K. Nishimura, J. Alloys Compd. 509 (2011) 1796.
[31] A.O. Pecharsky, Yu. Mozharivskyj, K.W. Dennis, K.A. Gschneidner Jr., R.W.
McCallum, G.J. Miller, V.K. Pecharsk, Phys. Rev. B 68 (2003) 134452.