Magnetocaloric effect and magnetic refrigeration

Anan bari Sarkar (151131)∗

Department of Physics, IIT kanpur
(Dated: April 7, 2017)

1. MAGNETOCALORIC EFFECT

1.1 Introduction

Magnetocaloric effect(MCE) is defined as the heating or cooling of the magnetic materials due to a varying magnetic
field .It is due to the coupling of the magnetic sublattice with the magnetic field , which changes the magnetic part of
the entropy of a solid.At constant pressure the entropy of a magnetic solid , S(T,H) is a combination of three different
terms , those are the magnetic SM , lattice SLat , and electronic SE1
S(T,H) = SM (T,H) + SLat (T) + SE1 (T) ..... (1)

FIG. 1:

In Fig 1. MCE for a ferromagnetic material in two constant magnetic fields is shown . If we apply magnetic field
adiabatically (i.e. keeping the entropy constatnt) , then it will give rise to a temperature rise ( ∆Tad = T1 - T0 ),
which is given by the horizontal arrow.MCE can also be visualized by means of isothermal magnetic entropy change
(∆SM = S1 - S0 ), which is given by the vertical arrow . Therefore MCE basically implies the change in temperature
(∆Tad ) and the change in magnetic entropy (∆SM ), those two are the functions of the initial temperature (T0 ) and
magnetic field change (∆H).
*** Raising Magnetic field ⇒ increases magnetic order ⇒reduces magnetic entropy ⇒
∆Tad (T,∆H) is positive ⇒ ∆SM (T,∆H) is negetive .
*** The signs of ∆Tad (T,-∆H) and ∆SM (T,-∆H) is correspondingly reversed when the mag-
netic field is reduced.

∗ Electronic address: sarkar@iitk.ac.in; URL: http://www.iitk.ac.in

 2

The ∆Tad and ∆SM can be calculated using the following formulas
RH
∆SM (T,∆H) = H12 ( ∂M∂T (T,H)
)H dH ...............(2)

and
RH
∆Tad (T,∆H) = - H12 ( T
C(T,H) )H ( ∂M∂T
(T,H)
)H dH .........(3)

from (2) and (3) equation we can see that both ∆Tad and ∆SM are dependent on ( ∂M∂T (T,H)
)H . For Ferromagnetic
particles | ( ∂M∂T
(T,H)
)H | is largest at curie temperature , implies that | ∆SM | will show peak at TC ,whereas ∆Tad
will show peak near TC when ∆H → 0.[As because from the C-T plot of ferromagnetic material one can see that
with increasing ∆H, the TM (the temperature ,at which the maximum of MCE occurs) shifts away from TC ]
But for paramagnet , MCE is significant only near absolute zero temperature, the reason
is that if the temperature is high, then increasing magnetic field will not result in a complete alignment of moments,
Hence ∆Tad will also be less .

1.2 Measurement of the magnetocaloric effect

MCE can be calculated by namely two ways 1) Direct techniques 2) Indirect techniques .
Direct measurement techniques can be carried out in two different ways . One is using direct thermal
contact between sample and temperature sensor ;the other one is non-direct techniques ,where the sensor is not
connected to sample .The measurement can be carried out on immobilized samples when the magnetic field change
is provided by charging/discharging the magnet or by moving the sample in and out of a uniform magnetic field
volume.The accuracy of the direct techniques depends on the errors in thermometry ,errors in field setting , the
quality of thermal insulation etc . It was repoted earlier that this errors can be in 5-10% range .With this techniques
we can only calculate the temperature change .
In indirect measurement we generally use Heat capacity measurement or magnetization measurement
to calculate ∆Tad and ∆SM . The accuracy of ∆SM calculated from magnetization data depends on the accuracy of
the magnetic moment ,temperature ,and magnetic field measurements .
The heat capacity measured as a function of temperature in constant magnetic fields ,C(T)H provides
the most complete characterization of magnetic materials .Once we know the heat capacities with different magnetic
fields then we can calculate the entropies corresponding to those magnetic fields by the following relations ;
RT
S(T)H = 0 ( C(TT )H )dT + S0 . Where S0 is the zero temperature entropy. For this process the error was reported
to be in range 3 -10 % .

1.3 Magnetocaloric effect in paramagnets

As we have mentioned earlier that MCE in paramagnets is significant only near absolute zero temperature . Although
with paramagnets we can reach to ultra-low temperature by adiabatic demagnetization cooling process .
Paramagnetic salts have low thermal conductivity ,which is not good for adiabatic demagnetization process
, therefore Paramagnetic intermettalic compounds were used now a days . It was reported that with PrNi5 we
can reach upto 27 µK at which useful measurement can be done on materials .But at higher temperature ( 3K < T
< 13K) the MCE in PrNi5 is anomalous due to the crystalline electric field effect, as a result of that it cools upon
magnetizing and warms upon demagnetization .
The reason for this anomaly can be described by taking into account the effect of crystalline electric
field effect(CEF) on the magnetic energy levels . Due to this CEF effects the 9-fold degenerate magnetic energy levels
split into several energy levels .. Two of those energy levels ( Γ4 (0) and Γ1 (1.50 meV) ) cross each other at Hc = 16T ,
at temperature(T)=0.3K . That means whenever H is increased upto 16T, the difference in the energy levels of Γ4 (0)
and Γ1 (1.50 meV) goes to zero, this implies density of states will be larger -implies the entropy will also increase with
increasing magnetic field [ Anomalous behaviour]. But as the magnetic field(H) increases above 16T , the energy
difference between the levels again increase , therefore density of states will be low , as a result of that entropy will
also be low [ Normal behaviour] .
Materials with high thermal conductivity ,low lattice heat capacity and very low ordering temperature are
very good for measurement of MCE . Therefore Paramagnetic Garnets are used . Also if the ordering temperature
is low then it is possible to obtain a large ∆SM to maintain a significant MCE . Noticeable MCE was observed with
 3

paramagnetic garnets ,such as neodymium gallium garnet(Nd3 Ga5 O12 ) and gadolinium gallium garnet (Gd3 Ga5 O12 )
.

1.4 Magnetocaloric effect and order-disorder magnetic phase transition

When spontaneous magnetic ordering occurs ,the magnetic ordering parameter as well as the bulk magnetization
of a solid undergo large changes in relatively narrow temperature interval close to curie/Neel temperature.
The 4f metals and their alloys are more useful in this case than the 3d metals and their alloys ,because the
theoretical magnetic entropy of the 4f metals are comperatively larger than 3D metals .

1.5 MCE in range 10 - 80 K

For this temperature range we generally use 4f metals like , Pr,Nd,Er,Tm.For Nd the MCE was reported earlier
and the results are ∆Tad ∼ 2.5K at T= 10K for ∆H=7T .
MCE in Nd,Er,Tm are generally low .The reason for this is that most of the magnetic phases in those
materials are antiferromagnetic and ferrimagnetic ,therefore much of the entropy is involved in flipping spins to a
ferromagnetic alignment .
The material which shows largest MCE in this temperature range are actually intermetallic compounds
containing lanthanides matels.

1.6 MCE in the range 80 -250K

MCE in this temperature range is not that great .The T/C vs T plot of a typical metallic material in this range
shows a minimum ,therefore the adiabatic heating and cooling would also be minimum in this temperature range .
Pure Dy is the best magnetic refrigerant materials for this temperature range with ∆Tad ∼12 K at 180K
for ∆H=7T .It was reported that the Gd5 (Six Ge1−x )4 alloys for 0.08 ≤ x ≤ 0.43 have extremely large ∆SM and ∆Tad
values .

1.7 MCE near room temperature

For this range the most used material is the Gd , which orders ferromagnetically at 294K . Different ∆Tad values
were reported for different TC values for different ∆H value at 10T . A variety of Gd alloys were prepared with
different lanthanide metals to improve the MCE .But all this addition just shift the curie temperature of Gd to lower
temperature without any noticeable improvement in MCE .Intermetallic compound with curie temperature above ∼
290 K show significantly lower MCE . Only the MCE of Gd5 Si4 with TC ∼ 335K approaches that of Gd .

1.8 The Giant MCE

A first order phase transition in a magnetic material implies discontinuity in entropy , means we will also have
discontinuity in magnetization , therefore | ( ∂M∂T
(T,H)
)H | may be infinitely large at the ordering temperature , giving
rise to a giant MCE .
The giant MCE was first observed in FeRh .This is due the first order transition from antiferromagnetic to
ferromagnetic alignment at ∼ 308K . This MCE was reported to be negetive with values as -13K for ∆H=2T . But
for FeRh the MCE is irreversible i.e MCE disappear after the first apllication of magnetic field .
Gd5 (Six Ge1−x )4 alloys ,where 0 ≤ x ≤ 0.5 was reported to display ∆SM at least two times larger than that
of Gd near room temperature . This alloys can be used as good magnetic refrigerant materials ,the reasons can be
,First the curie temperature of those alloys can be tuned between ∼ 20K to ∼ 286K by varying the Si to Ge ratio and
by introducing small alloying additions of Ga to Gd5 (Si2 Ge2 ) ; Second the MCE for those materials are reversible.
The reasons for the large magnetocaloric effect in Gd5 (Si2 Ge2 ) are (i) a small temperature dif-
ference between the two magnetic phase transitions (ii) an inequivalent distribution of the magnetic entropy between
the first order and the second order transitions , with bulk of the entropy being utilized in the first order one; and (iii)
 4

the fact that the transition thermodynamically remains a first order phase transformation with increasing magnetic
field.
The difference in MCE for FeRh and Gd5 (Six Ge1−x )4 alloys is associated with the nature of the first order
phase transition . For FeRh , it is a magnetic order-order transition. But for Gd5 (Six Ge1−x )4 we have two different
types of transitions , those are magnetic transition and crystallographic order-order transition .
The crystallographic phase transition takes place from orthorhombic structure to the monoclinic structure
. Whereas for magnetic transitions; a second order transition takes place from paramagnetic to ferromagnetic(I) ,
followed by a first order transition from high temperature ferromagnetic(I) to ferromagnetic(II) .
The reason behind the irreversibility or reversibility in MCE of FeRh and Gd5 (Si2 Ge2 ) re-
spectively can be described as :- the low temperature phase of FeRh is an antiferromagnet and the high temperature
phase is a ferromagnet, which combined with a large thermal hysteresis ( ∼ 10-12 K) between the transition on
warming and on cooling and the probable large volume changes during the transition, causes the irreversibility of the
magnetocaloric effect with regard to alternating magnetic field (i.e., it disappears after one cycle). But the width of
the thermal hysteresis in Gd5 (Si2 Ge2 ) transition is much narrower (∼ 2K) Furthermore, cycling of a magnetic field
does not induce an irreversible change in the magnetic and magnetocaloric behaviors of Gd5 (Si2 Ge2 ).

2. MAGNETIC REGRIGERATION

2.1 Thermodynamic cycle

The thermodynamic cycle, used for Magnetic refrigeration is analogous to Carnot refrigeration cycle , only difference
is that for magnetic case , one increases or decreases the magnetic field instead of pressure . the diagram of the cycle
is given below .

FIG. 2: Refrigeration cycle

Initially magnetic field is apllied adiabatically to the refrigerant material, as a result of that all the moments
will try to align along the field direction, therefore the energy of the system will decrease, as a result of that temperature
of the system will increase .
The extra heat can be removed by placing the system in contact with any fluid or gas .
 5

After removing the extra heat from the system , the system is demagnetized adiabatically , therefore all the
moments will try to randomize themselves ,this randomization needs energy, this energy is provided by the system,
therefore the system cools .
after that the magnetic field is held constant to prevent the material from reheating. Then the material is
placed in thermal contact with the environment to be refrigerated.

2.2 Active Magnetic regenarator cycle

Regenarator : It is a type of heat exchanger where heat from the hot fluid is stored at irregular interval
in a thermal storage medium before it is transferred to the cold fluid .
For the AMR cycle ,which is described below ; a porous bed of a magnetic refrigerant materials is used ,this
materials acts as both the refrigerant that produces refrigeration and the regenerator for the heat transfer fluid . The
details of the AMR cycle is given below .

FIG. 3: The four steps of AMR, (a) magnetization, (b)flow from cold to hot, (c) demagnetization, (d) flow from hot to cold

Let us to assume that we are working between two temperature limit, where the hot exchanger is at
75◦ F(∼24◦ C) and the cold heat exchanger is at 40◦ F(∼5◦ C) . The temperature profile for the bed in absence of any
magnetic field is given in Fig 3a. by the dashed line , now when a magnetic field is applied to the refrigerant, then
the moment will align along the field direction , as a result of that,the energy of the system will decrease, results in a
increase in the temperature(∆Tad ),which form the final magnetized bed temperature profile ,given by the solid line
in fig 3a. Therefore the final temperature of the bed is 24◦ C + ∆Tad .
Now the 40◦ F(∼5◦ C) fluid flows through the bed from the cold end to the hot end (Fig 3b).This flow
cools the bed ,lowering the temperature profile,given by the temperature profile of Fig 3b , the fluid in tern is heated
at temperature 24◦ C + ∆Tad by the bed, therefore the fluid emerging at a temperature ,higher than 24◦ C , thus heat
is removed from the fluid at the heat sink ,thereby increases the temperature of the hot heat exchanger .
 6

After the bed is cooled at temperature 5◦ C , the magnetic field is removed . Then the moments will
try to align randomly , this process needs energy . This energy will be provided by the Bed , results in a decrease in
temperature by ∆Tad . Therefore after the complete removal of the magnetic field , the bed will be at a temperature
5◦ C - ∆Tad . The temperature profile of the bed is given by the dashed line in Fig 3c .
Now the 24◦ C fluid is allowed to flow from the hot to the cold end of the bed , where the fluid emerges
from the bed at a temperature (5◦ C - ∆Tad ) , thus lowers the temperature of the cold heat exchanger .
By repeating this cycle we can increase the temperature of the heat exchanger , also we can decrease the
temperature of the cold heat exchanger more and more , thus we can create a high temperature difference between
the hot and cold heat exchanger .

Positive features of AMR : First , As the MCE of the individual particle changes the entire temperature profile
across the bed , therefore in this AMR cycle we can achieve greater temperature span ,compared to temperature span
, achieved by the MCE of magnetic refrigerant materials.
Second , in this case the heat is transferred between the solid particles of a single bed , not between two different
solid assemblies .
Third, We can use a bed ,made of different layers of magnetic materials , as for AMR cycle , each particle donot
experience the entire temperature span .

2.3 Recent achievements in near room temperature

Recently a magnetic refrigeration process was reported by Zimm et al. , this MR process operates near room
temperatures in a magnetic field between 1.5 T to 5 T and uses 3 kg of Gd spheres packed in two magnetocaloric beds
. Water was used as heat transfer fluid .It was reported that it can generates upto 600 W power in a 5T magnetic
field .The maximum cooling power and coefficient of performance were reported for a temperature span equal to
approximately 13 of the maximum observed temperature span of 38◦ C for ∆H= 5 T .

3. REFERENCES

1) Magnetocaloric e!ect and magnetic refrigeration by Vitalij K. Pecharsky, Karl A. Gschneidner Jr.

2)Anomalous behavior of the magnetic entropy in PrNi5 – by P. J. von Ranke ,V. K. Pecharsky , K. A. Gschneidner,
Jr and B. J. Korte .

3)Giant Magnetocaloric Effect in Gd5 (Si2 Ge2 ) by V. K. Pecharsky and K. A. Gschneidner, Jr.

4) Magnetocaloric effect and heat capacity in the phase-transition region by A. M. Tishin, K. A. Gschneidner, Jr.
and V. K. Pecharsky .