Magnetic Properties of Materials

Magnetism is virtually Universal

 “Magnetic Properties of Solid Materials”

Reading:

(1) P.W. Selwood, Magnetochemistry, 2nd Ed., Interscience Publishers, Inc.: New

York, 1956.

(2) R. L. Carlin, Magnetochemistry, Springer-Verlag, Berlin, 1986.

(3) Charles Kittel, Introduction to solid state physics, Wiley, 2015

(4) Electronic Structure and Magnetism of Inorganic Compounds, Chemical Society

(London), vol. 1-7 (1970-1982).

2
 What is a Magnetic Material ?

A material is said to be magnetic material if it can alter the magnetic flux density
when placed in an external magnetic field, H.

Magnetic Flux in
Magnetic Flux in presence of a Magnetic Material
vacuum
 Origin of Magnetism

Macroscopic Origin
If a loop of area A is carrying a current I, the
intrinsic intensity of the magnetic field is
given by the magnetic moment vector (m)
directed from the north pole to the south pole.

The magnetic moment is the measure of the strength of the magnet and is the ability to be
affected by an external magnetic field H.
Magnetic Moment Vector (m). |m| = IA, Magnetic field strength/Magnetizing force (H).
(Measure of the strength of the externally
applied field).
Units: [Am2] or [Joule/Tesla].
Units: [A/m]
 Origin of Magnetism
Atomic Origin of Magnetic Moment

Microscopic Origin of Magnetism

i) Nuclear spin (which is slow and small contribution to the overall magnetic effect)
ii) Spin of electrons
iii) Orbital motion of electrons around the nucleus

The magnetic moment due to spin is equal to the magnetic moment due to orbital motion
(in the first Bohr orbit) and is approximately expressed in terms of the Bohr magneton (B):
 Magnetic Effect

Magnetic effects are determined by measuring the response to an external magnetic field H,
which sets up a magnetic induction B within the macroscopic body.

B = H + 4M Gaussian (cgs) units

B = 0(H + M) MKS (SI) units

INDUCTION FIELD MAGNETIZATION
(Flux Density) (Field Intensity)

Vacuum (M = 0) Paramagnetic Diamagnetic

Substance Substance
6
 Magnetic Effect

M measures the materials response to the applied field H

Or M is the magnetization induced by the applied external magnetic field H.

Magnetization (M) = magnetic moment (m) per unit volume (V).

M = m/V
Units: [A/m]

Magnetic induction/Magnetic flux density (B) = Magnetic flux per unit area

B is the magnetic flux density inside the material

Units: [Tesla = Weber/m2]

 Magnetic Induction vs. Magnetic Field

B = H + 4M (In CGS system)

μ= and χv =

μ = 1 + 4χv  (Permeability): Measure of concentration of lines of

force per unit area compare to that in the vacuum
cv (Volume Susceptibility): measure to which the material is susceptible or
sensitive towards the external magnetic field

c  M/H (the symbol cv is also used to emphasize that the quantity is per unit volume)

Units: [dimensionless]

Gaussian Units MKS Units

B = H and M = cvH B = H + 4M B = 0(H + M)
H = H + 4cvH H = 0(H + cvH)
 = 1 + 4cv  = 0(1 + cv)
cv = ( - 1)/4 cv = (/0) - 1
Magnetic Susceptibility

Gram Susceptibility: cg = cv / Density

Molar Susceptibility: cM = cg  FW (FW = formula weight)
= cv  FW / Density

μ = 1 + 4χv

Diamagnetism:  < 1;
Paramagnetism:  > 1;
Ferromagnetism:  >> 1;
Superconductors:  = 0;

Vacuum (M = 0) Paramagnetic Diamagnetic

Substance Substance
9
Magnetic Moment

Magnetization: M = cM H; Magnetic Moment per unit Volume

 Q
m = I(R2) n = L
R Q 2m
I = current

S i mi
M=
V
(A/m)

When a magnetic moment (“dipole”) is placed in an induction field, it experiences a

torque (“turning effect”) and develops a potential energy:
B = Bz

Torque: =mB m
q
Potential Energy: Vmag = -m  B = -mB cos q  -mzB
(J) (Am2)(T)

10
Units

Symbol Name Gaussian Unit MKS Unit Conversion

Induction;
B Gauss (G) Tesla (T) (Weber/m2) 1 T = 104 G
Flux Density
H Field Oersted (Oe) Ampere/meter (A/m) 1 A/m = 4/103 Oe
Magnetization;
1 A/m = 10-3
M Magnetic Moment emu/cm3 A/m
emu/cm3
per Volume
m Magnetic Moment emu Am2 1 Am2 = 103 emu
Volume Dimensionless 4 (MKS) = 1
cv Dimensionless
Susceptibility (emu/cm3) (Gauss)
1 m3/kg = 103/4
cg Gram Susceptibility cm3/g = emu/g m3/kg
emu/g
1 m3/mol = 106/4
cM Molar Susceptibility emu/mol = cm3/mol m3/mol
cm3/mo
Permeability of Free 4  10-7 H/m = 1
0 Dimensionless Henry/m (H/m)
Space (Gauss)

11
Magnetic Susceptibilities of Elements (T = 300 K)
Data taken from CRC Handbook of Chemistry and Physics,
92nd Edition, 2011-2012 (On-line); Section 4.
-1
10 cm (cm3/mol) Tb
-2 Fe, Co, Ni
10
-3 Tm
10 Nd
-4 O
10 Pd
Sc Sm Pu
-5 La Lu Pt
10 Th
Cs Yb
-6 Li Al
10 K Rb Paramagnetic

-10
-5
Be Ne
Cu
Ag Diamagnetic
Au
-4 Si Ar Kr Xe
-10
Bi
-3
-10
0 10 20 30 40 50 60 70 80 90 100
Z 12
Types of Magnetic Order

Diamagnetism Ideal Paramagnetism

Antiferromagnetism
Ferromagnetism

Ferromagnetic
 Types of Magnetic Order
Ferrimagnetism

Ferrimagnetic

Type of Magnetism ( strength/magnitude)

Weak Strong
Diamagnetic & Ferromagnetic,
Paramagnetic Materials Antiferromagnetic &
Ferrimagnetic Materials
Diamagnetism and Paramagnetism

Diamagnetic and paramagnetic materials are very weakly magnetic and show
linear (and isotropic) behavior, so that M, H, and B are all proportional.

B =  H and M = cv H (cv =
M
H )

N2(liquid) O2(liquid)
Paramagnet
Diamagnet

15
 Diamagnetism

The presence of closed shells of electrons and orbital motion of electrons.

Larmor theorem
Diamagnetism in molecular, semiconducting, insulating materials.
Landau theory
Diamagnetism in metals.

(i) Larmor theorem

The motion of electron around the nucleus creates magnetic field opposed to
the applied field (Lenz’s Law)
Larmor frequency of electron ,w = eB/2me
Time for one revolution = 2/w = 4me/eB
I = (charge)/(revolution per unit time) = −e/(4me/eB)
I = − e2B/4me
Diamagnetism (Larmor theorem)

Magnetic moment m of a current loop by electron = IA

A = r2 = area of the loop
m = I (r2) = − r2) = − r2(0H)

r2 = x2 + y2 = mean square of the perpendicular distance of the electron

from the magnetic field axis through the nucleus.

The mean square distance of electron from nucleus, r2 = x2 + y2 + z2

For spherically symmetric, x2 = y2 = z2

So, r2 = 2/3 r2

mdiam = - e2 r2 (0H)

6me

e2 2
cdiam = - 6mer  0 For single electron
Diamagnetism
Larmor (Langevin): Molecular, semiconducting, insulating materials
e2
cdiam (m3/mol) = -NA 6m Zr2 0

• cdiam is a constant and has a smaller magnitude (10-6 emu/mol).

• Independent of H;

• Temperature independent

• Always negative (Lenz’s Law);

• present in all form of matter;

• All noble metal atoms are diamagnetic.

• Relative Permeability , μr < 1

18
Diamagnetic Susceptibilities
Larmor (Langevin): Molecular, semiconducting, insulating materials
e2
cdiam (m3/mol) = -NA 6m Zr2 0

(10-6 emu/mol)
Li+ -1.0 Be2+ -0.4 B -7.0 C -6.0 N ca. -5.0 O -4.6 F- -9.1
Na+ -6.8 Mg2+ -5.0 Al3+ -2.0 Si -13.0 P -26.3 S -15.0 Cl- -23.4
K+ -14.9 Ca2+ -10.4 Ga3+ -8.0 Ge4+ -7.0 As5+ -6.0 Se -23.0 Br- -34.6
Rb+ -22.5 Sr2+ -19.0 In3+ -19.0 Sn4+ -16.0 Sb5+ -14.0 Te -37.3 I- -50.6
Cs+ -35.0 Ba2+ -26.5 Tl3+ -31.0 Pb4+ -26.0 Bi5+ -23.0

Sc Ti V Cr Mn Fe Co Ni Cu Zn (10-6 emu/mol)
+1 -12
+2 -15 -15 -14 -13 -12 -12 -11 -15
+3 -6 -9 -10 -11 -10 -10 -10
+4 -5 -7 -8 -8

19
G.A Bain, J.F. Berry, J. Chem. Educ. 2008, 85, 532-536.
Diamagnetic Susceptibilities

cdiam = Si cdiam(i) Diamagnetism is additive in nature

All measurements should be corrected for diamagnetism cobserved = cpara + cdiam
(+) (-)
cdiam(i) (10-6 emu/mol)
C (ring) -6.24
5 C (ring) = 5(-6.24  10-6) = -31.2  10-6
N (ring) -4.61
H -2.93 1 N (ring) = 1(-4.61  10-6) = -4.6  10-6
H
5 H = 5(-2.93  10-6) = -14.7  10-6
H C H
Total: -50.5  10-6 emu/mol
C C

C C Exp’t: -49  10-6 emu/mol

H N H

20
Landau theory - Pauli Principle
Landau Diamagnetism is induced for the conduction (valence) electrons of metals
by Lenz’s Law, which induces electron motion.
For metals having free electrons χ T0 (it is inverse for paramagnetic
materials).
Landau susceptibility comes from the spatial motion of the electrons and it is
independent of the spin. However susceptibility comes from the spin
interaction with the magnetic field was included in Pauli susceptibility.

So the Landau theory for free electron model is not appropriate for metals.
The Pauli principle needs to be taken into account.

the temperature independent Pauli susceptibility:

Free Electrons under magnetic field

χP = N[3μ0μ2B/2kBTF]

Free Electrons: cLandau = -cPauli/3

 Paramagnetism

It originates from the spin and orbital motion of unpaired electrons present
in the material.

Interaction with the External Magnetic Field:

When placed in an external magnetic field these materials are attracted

towards the field.
 Paramagnetism

Magnetic moment of an atom or ion in free space is given by = gJ B J

gJ is Landé g-factor

J (J + 1) + S (S + 1) - L (L + 1)
gJ = 1 +
2J (J + 1)
J = Total electronic L is the orbital angular momentum, and
angular momentum) S is the spin angular momentum.

(J = total angular momentum quantum number

B = 9.2740  10-24 J/T
=│L + S│ for orbitals more than half filled )
(Bohr magneton) = │L −S│ for orbitals less than half filled

Saturation magnetic moment: Maximum value of the moment by aligning all

dipoles with a field (high field strength, low temperature).

Magnetic Field H || z = gJ B Jz
“Spin-Only”: sat = 2 S B
Or, sat = gJ Jz B
 Paramagnetism

Effective magnetic moment: eff = |mpara| = gJ [J (J + 1)]1/2 B

J (J + 1) + S (S + 1) - L (L + 1)
gJ = 1 + 2J (J + 1)

“Spin-Only”: eff = 2 [S (S + 1)]1/2 B

sat < eff. (When Orbital Angular Momentum is quenched…)
eff  2 S  S  1  B  n  n  2  B n = # of unpaired electrons

“SPIN-ONLY”
dn Examples J = gJ [J(J+1)]1/2 S = 2[S(S+1)]1/2 eff (exp)
d1 Sc, Ti3 1.549 1.732 1.7-1.8
d2 Ti, V3+ 1.633 2.828 2.6-2.8
d3 V, Cr3+ 0.775 3.873 3.8
d4 Mn3+, Ru4+ 0.000 4.899 4.9
d5 Mn, Fe3+ 5.916 5.916 5.9
d6 Fe, Co3+ 6.708 4.899 5.1-5.5
d7 Co, Co2+ 6.633 3.873 4.1-5.2
d8 Ni, Ni2+ 5.590 2.828 2.8-4.0
d9 Cu2+ 3.550 1.732 1.7-2.2
(Units of B)
 Paramagnetic Atoms and Ions

Transition Metals (d n)

6
Magnetic Moment

5 J (J + 1) + S (S + 1) - L (L + 1)
gJ = 1 + 2J (J + 1)
4

1  J Calculated
 S Calculated
0  eff Experimental

0 1 2 3 4 5 6 7 8 9 10

Electrons in the d Subshell

Spin-Only Moment is a good approximation for transition metals

Orbital angular momentum often quenched

25
Paramagnetic Atoms

Lanthanide Metals (f n)

10

8
Magnetic Moment

 J Calculated
2
 S Calculated

0  eff Experimental

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Electrons in the f Subshell
Must include spin-orbit coupling

Largest deviations for f 5 and f 6

26
Temperature Dependence of Magnetization

Magnetic susceptibility measurements are bulk property measurements

Results are averages over the ensemble of molecules in the system in thermal equilibrium

 i exp  - Ei / kT  Probability that an energy level with

Statistical Averaging: pi 
 i exp  - Ei / kT 
i
energy Ei is occupied…

(Boltzmann Distribution)
(Boltzmann distribution function)

Now, we must calculate the average magnetic moment for a paramagnetic ion:

  exp  - E / kT 
i i i
m   pi i  i

i  exp  - E / kT 
i
i i

Molar Magnetization: M = NAm

Potential Energy: Emag = -m  B (m = magnetic moment, B = magnetic induction)

27
 Temperature Dependence of Magnetization

High temperature / Low field:

Low temperature / High field:

eff  g J J  J  1  B
2
𝐴 𝑒𝑓𝑓 M = NA gJ J B = Msat

2
𝑀
𝐴 𝑒𝑓𝑓 B = 9.2740  10-24 J/T (Bohr magneton)

Curie’s Law: Susceptibility is inversely proportional to temperature

C
cM  Where
T
Or, C = 0.1252eff
0.125eff2
cM  1  8 
T  2  T
c M  eff 
c MT  0.125eff2

28
 Temperature Dependence of Magnetization

“Example”: Cr3+ (d 3)
S = 3.873 B (g = 2.00)

0.5 2.0
c c
cT
0.4
0.125eff2 1.5
cM  1  8 
0.3 T  2  T
c M  eff  1.0 c MT  0.125eff2
0.2

0.1 0.5

0.0
0.0

0 50 100 150 200 250 300 0 50 100 150 200 250 300
0 50 100 150 200 250 300

T (K) T (K) T (K)

eff  8c MT
 2.828 c MT
29
Temperature Dependence of Magnetization
c

Slope = 8/μ2eff = 1/C C = 0.1252eff  8 

1
 2  T
c M  eff 
μeff =

0 50 100 150 200 250 300

T (K)

dn Examples J = gJ [J(J+1)]1/2 S = 2[S(S+1)]1/2 eff (exp)

d1 Sc, Ti3 1.549 1.732 1.7-1.8
d2 Ti, V3+ 1.633 2.828 2.6-2.8
d3 V, Cr3+ 0.775 3.873 3.8
d4 Mn3+, Ru4+ 0.000 4.899 4.9
d5 Mn, Fe3+ 5.916 5.916 5.9
d6 Fe, Co3+ 6.708 4.899 5.1-5.5
d7 Co, Co2+ 6.633 3.873 4.1-5.2
d8 Ni, Ni2+ 5.590 2.828 2.8-4.0
d9 Cu2+ 3.550 1.732 1.7-2.2
Non-Ideal Paramagnets: Deviations from the Curie Law
C Curie Constant
Curie-Weiss Law: cM  C  0.125eff
2
T -q Weiss Constant

1 q  Curie
c   T -  
-1
M
(Paramagnetic)
C  C 

Antiferromagnetic Ferromagnetic AFM and FM effects are

Interatomic.
T
q<0 q=0 TN TC q > 0

31
 IMPORTANT EQUATIONS

Effective magnetic moment: eff = |mpara| = gJ [J (J + 1)]1/2 B

Spin only magnetic moment eff  2 S  S  1 B  n  n  2   B

Saturated magnetic moment: sat = gJ Jz B

C (C =Curie Constant = 0.1252eff
Curie’s Law: cM 
T
c
1  8  1  8 
 [(1/C)]T
2 
T  2  T
 
c M  eff  c M  eff 

μeff =

0 50 100 150 200 250 300

T (K)
 Strong Magnetism or Nonlinear Response (FM, AFM)

Ferromagnetism (FM)
Ferromagnetic materials exhibit nonlinear response to external magnetic field, and
their magnetization depends on their previous history.

M = cv H (Not valid for Ferromagnet)

A ferromagnet has spontaneous magnetic moment- A magnetic moment even without

applied magnetic field due to electron spins are arranged in a regular manner.

The alignment of electron spin in an ordered manner is due to exchange interaction.

The exchange energy (Heisenberg Model):

Hex = −2J Si.Sj (J = exchange integral, related to overlap of charge

distribution of the atoms i and j, and S is the spin angular
momentum. J>0 for ferromagnet, J<0 for antiferromagnet. 33
Strong Magnetism or Nonlinear Response (FM, AFM)

The Curie temperature (Tc) is the temperature above which the spontaneous
magnetization vanishes and goes to paramagnetic state.

Tc (Fe) = 1043 K
Tc (Co) = 1388 K
Tc (Ni) = 627 K
 Mechanism of Ferromagnetism

In Ferromagnetic materials, the atoms form domains. Domain is a region

inside a material where group of magnetic moments naturally align in the
same direction.
 Ferromagnetism

Saturation
Magnetization
Remnant magnetization (Remanence):
Mr = Mfor H = 0.

The amount of magnetization retained

at zero external field

Coercive Force:
Hc = Hfor M = 0 (reverse magnetic field
needed to reduce M to zero. Hysteresis Loop
Hysteresis Loop
The negative magnetic field require to demagnetize

Once the magnetic domains are reoriented , it takes some energy to turn them back
again. This property of ferromagnetic materials is useful as a magnetic memory.
Some ferromagnetic materials will retain an imposed magnetization indefinitely and
are called as permanent magnets.
36
Mechanism of Ferromagnetism
Application of Ferromagnetism
Application of Ferromagnetism

Large Coercivity: Permanent Magnet (Ex: SmCo5; Coercivity= 6 x 105Am-1

Pure Fe; Coercivity = 50 Am-1)

Small Coercivity: Electrical motor, Magnetic refrigeration etc..

 List of Ferromagnetic materials

3d 6 band
3d 7 ferromagnet
3d 8

7
simple
4f
ferromagnet

Cause for non-integral nB :

• spin-orbit interaction; local magnetization of conduction e; ferrimagnetism
 Magnetism in Metals

Usually Ferromagnets are metals and Antiferromagnets are insulators.

T = 300 K
H He

Li Be B C N O F Ne

Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac Rf Db Sg Bh Hs Mt 110 111 112

Lanthanides: Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Actinides: Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

Diamagnetic Ferromagnetic

Paramagnetic Antiferromagnetic
List of Ferromagnetic materials

Cause for non-integral nB :

• spin-orbit interaction; local magnetization of conduction e; ferrimagnetism
 Understanding of ferromagnetism in metal

(i) Assuming that moments are localized to atoms,

Hex = −2 J Si.Sj (J = exchange integral, related to overlap of charge
distribution of the atoms i and j
Si and Sj are the spin momentum for electron i and j
J = positive for FM

(ii) using the band structure of metals (giving rise to itinerant electrons).

Localized electrons contribute to ferromagnetism not the free electrons.

4s electrons are free and do not contribute to FM
3d electrons in transition metals are neither fully localized nor fully free
Example: Fe saturation magnetic moment/atom = 2.2 B
3d + 4s = 8 e (~ 0.95 is free)
 Understanding of ferromagnetism in metal
Zeeman
E E Splitting
sp-band

Hext
EF
d-band
EF
N(E) N(E) 2BHext
N(E) = N(E) = N(E)
N(E) N(E)

Fe (NM)
6
N  N  - N   2  B H ext N  EF 
4
6

Fe (FM): m = N - N
2
4
0
2
(eV) -2
0
-4
-2
-6
-4
-8
-6
-10
-8

-10
 Understanding of ferromagnetism in metal

Stoner Criterion

FM: I / W  0.2  IN  E   1
F
-1
AFM: I / W   103 N d 10 - N d  

I = Intra-atomic Exchange Energy

W = Bandwidth of Nonmagnetic State
 Antiferromagnetism
Antiferromagnetism first predicted by Néel, 1936

Spins are ordered in an antiparallel arrangement

Has zero net magnetic moment at temperature below the ordering temperature (TN)

Not easy to show that it is a AFM. First confirmed by Shull in 1949 using neutron
scattering.

Types of Antiferromagnetic ordering

M =saturation moment = 0 M =saturation moment 0 M =saturation moment 0

 Types of Simple (Collinear) AFM
In the simple (collinear) AFM the spins are arranged three different types.

A-Type:
The intra-plane coupling is ferromagnetic while inter-plane
coupling is antiferromagnetic.

C-type:
The intra-plane coupling is antiferromagnetic while inter-plane
coupling is ferromagnetic.

G-type:
Both intra-plane and inter-plane coupling are antiferromagnetic.
 Temperature dependence of susceptibility in AFM

c / / T  0   0
c T  TN c c T(T
T=T0)
N N= cT T  TN
T N

MnF2 c / / T  TN   c  T  TN 

For polycrystalline sample averaged

susceptibility cP(T) near 0 K:

cP(T = 0) = [cz + 2cxy]/3 [where cxy = c(TN)].

cP(T = 0) = 2/3c(TN)
 Neutron diffraction on AFM materials
Neutron

Spins on single (111) plane are //.

Spins on adjacent (111) planes are anti-//.
 Understanding of Antiferromagnetism

The exchange energy (Heisenberg Model):

U = −2JSi.Sj (J = exchange integral, related to overlap of charge
distribution of the atoms i and j
J = negative for AFM ordering
Advanced Topics

Magnetoresistance

Magnetocaloric Effect (Room temperature Refrigeration)

 Magnetoresistance
Relative change in electrical resistance of a material on the application of
magnetic field.
𝐻 0 RH and R0 are the resistance of the
0 sample at a magnetic field H and H = 0
Depending on the magnitude, it is called either as Giant magnetoresistance(GMR) or
Colossal magnetoresistance(CMR).
GMR/CMR
Discovered in 1988 and was commercialized in 1996 as reading heads and data storage.
Revolutionize hard drive and data storage devices in computer.
Nobel Prize in Physics 2007
Peter Grunberg
Albert Fert
 Background

Ordinary magnetoresistance (OMR) discovered in 1856 by Lord Kelvin.

Resistance of iron changes up to 5% with external magnetic field.

Little Progress on MR till 1980.

In 1988, Fe/Cr/Fe multilayer thin film were fabricated and shows 50% MR effect

Fe
Cr
Fe

In 1993, Collosal magnetoresistance (CMR) discovered in Mn based perovskite oxides.

Order of magnitude change in resistance

 Mechanism of GMR (Spin Dependent Scattering)

GMR materials are multilayers composed of alternating FM and nonmagnetic

(not a FM or AFM at room temperature) conducting layer.

In FM materials, resistance is greatly affected

by scattering of electrons on the magnetic
sublattice.
Scattering depends on the relative orientations
of the electron spins and those magnetic
moments

More scattering  higher electrical resistance

Electron spin and atom magnetic moments in

parallel  Weak scattering
Low resistance High resistance
Electron spin and atom magnetic moments in
antiparallel  Strong scattering
 Mechanism of GMR (Spin Dependent Scattering)

Higher DOS of 3d states  Stronger scattering

3d DOS at EF larger for minority spin than majority spin
Magnetoresistance (MR) in Perovskites

La0.9Sr0.1MnO3 (CMR)

LaMnO3 (AFM, no CMR)

SrMnO3 (AFM insulator) MR effect of Sn-doped InSb single crystal
thin film

Applications:
1. Read data in hard disk drives
2. Biosensors
3. microelectromechanical systems
𝐻 0

0
Magnetocaloric Effect (Room temperature Refrigeration)
 A Brief History of Magneto Caloric Effect (MCE)

Change in temperature of a suitable material is caused by exposing the

material to a changing magnetic field.
A magnetic solid heats up when magnetized and cools down when demagnetized.

Originally discovered in iron by E Warburg in 1881.

Thermodynamics of MCE was understood independently by Debye (1926) and
Giaque( 1927). Both of them suggested that MCE could be used to reach low
temperature (magnetic refrigeration) in a process known as adiabatic
demagnetization.
An adiabatic demagnetization refrigerator was constructed and utilized by Giauque
and McDougal (1933) to reach 0.53, 0.34 and 0.25K starting at 3.4 , 2.0 and 1.5K,
respectively using a magnetic field of 0.8T and 61g of Gd2(SO4)3.8H2O as the
magnetic refrigerant.
In 1997, Prof. Karl A. Gscheidner, lowa State University at Ames Laboratory
demonstrated the first near room temperature magnetic refrigerator
 Mechanism of Refrigeration in MC Materials

Adiabatic Magnetization

Isomagnetic Enthalpy Transfer

Adiabatic demagnetization

Isomagnetic Entropic Transfer

 Mechanism of Refrigeration in MC Materials

Adiabatic Magnetization

Substance placed in insulated environment

When a magnetic field applied, magnetic dipoles are aligned T + ΔTad

There is decrease in (magnetic) entropy  increase in temperature (T + ΔTad)

Isomagnetic Enthalpy Transfer

Added heat removed by a fluid like water or helium (-Q)

After a sufficient cooling Magnetocalric material and coolant are separated(H=0)

Magnetic Field held constant to prevent the dipoles from reabsorbing the heat
 Mechanism of Refrigeration in MC Materials

Adiabatic demagnetization

Magnetic field is removed

Sample cools down due to increase in entropy (disorder of the magnetic dipoles)

Isomagnetic Entropic Transfer

Material is placed in thermal contact with the Environment being refrigerated

Because the working material is cooler than
the refrigerated environment, heat energy
migrates into the working material (+Q)

Once the refrigerant and refrigerated environment

are in thermal equilibrium, the cycle continue
Mechanism of Refrigeration in MC Materials
 Suitable MC materials for refrigeration

Two quantitative characteristics of MCE :

Isothermal entropy change,

H2
 M 
S magnetic T   H  T  dH
1 H
Adiabatic temperature change,
H2
T  M 
Tadiabatic -   dH
H1
CH , p (T )  T  H

The material should have large (M(T,H)/ T)H and low C

Large (M(T,H)/ T)H  Large MCE

(M(T,H)/ T)H is large for a ferromagnet near its Curie temperature ( TC ).

So, one needs a ferromagnetic material with TC around RT

Frustrated magnet for adiabatic demagnetization cooling to milli-Kelvin
temperatures

Cooling process of a conventional paramagnet (left) and a frustrated magnet with impeded
magnetic order (right)
 Requirement for RT refrigeration

Ferromagnetically order near room temperature (RT).

Large magnetic entropy (large number of unpaired electron).

Nearly zero magnetic hysteresis (it is related to the working efficiency of a

magnetic refrigerant material).

Very small thermal hysteresis (this is related to the reversibility of the MCE of a
magnetic refrigerant material).

Large thermal conductivity (rapid heat exchange).

 Examples

Gd with TC around 290K is a potential MCE material for RT refrigeration.

In 1998 Ames Lab. Iowa + Astronautics Technology Center in Madison,

Wisconsin, USA demonstrated a magnetic refrigeration unit that operated at
room temperature.

However, the device required a cryogenically cooled superconducting magnet,

making it impractical for homes. Also Gd is costly!

Materials with giant MCE: Newer Promise

Gd5(GexSi1-x)4 alloys ; discovered in late 1990s.

TC around room temperature ;MCE 2-4 times larger than Gd.
 Room temperature magnetic refrigeration

Applications
Magnetic household refrigeration appliances.
Magnetic cooling and air conditioning in buildings.
Cooling in food industry and storage.
Refrigeration in medicines.

Benefits over the conventional refrigeration

Gas-free and high-efficiency green technology
Simple design technology
Low operating cost
Compactness