MME 467: Ceramics for Advanced Applications

Lecture 16-17
Magnetic Properties of
Ceramic Materials
Callister, Materials Science and Engineering- An Introduction.

Md. Rafiqul Islam

Lecturer, MME, BUET.

• Magnetic dipole
• Magnetic field strength, H
• Magnetic flux density/ induction, B
• B= H
• Permeability
• B0 = 0H
• r= /0
• Relative permeability
• B= 0 H + 0M
•In the presence of an H field, the magnetic moments within a material
tend to become aligned with the field and to reinforce it by virtue of their
magnetic fields; the term oM
• M= XmH
• X = r 1
 Origin of magnetism

One is related to its orbital motion around

the nucleus; being a moving charge, an
electron may be considered to be a small
current loop,

Generating a very small magnetic field,

and having a magnetic moment along its
axis of rotation.

Each electron may also be thought of as

spinning around an axis; the other magnetic
moment originates from this electron spin,
which is directed along the spin axis.
 The electronic wave function of the individual atoms/cations should
overlap directly (ferromagnetism) or indirectly (ferri-magnetism).

 The participating atoms /cations should have magnetic moments as a

result of partially filled inner electronic shells.

Fe: [Ar]3d64s2
Important magnetic materials are Fe,Ni,Co,Gd,Ho (metallic) and
Fe3O4(Feo.Fe2O3)and all ferrites.
The most fundamental magnetic moment is the Bohr magneton, B which is of
magnitude 9.27 x10-24 Am2
Comparison of the Electron Configurations and
Unpaired Electrons for Various Ions
Ion Electron Number of Magnetic moment in
Configuration Unpaired Electrons Bohr magneton (B)

Mg2+ 2p6 0 0
Al3+ 2p6 0 0
O2- 2p6 0 0
Sc3+ 3p6 0 0
Ti4+ (Ti3+) 3p6(3d1) 0(1) 0(1)
V3+ (V5+) 3d2(3p6) 2(0) 2(0)
Cr3+ (Cr2+) 3d3(3d4) 3(4) 3(4)
Mn2+ (Mn3+)(Mn4+) 3d5(3d4)(3d3) 5(4)(3) 5(4)(3)
Fe2+ 3d6 4 4
Fe3+ 3d5 5 5
Co2+ (Co3+) 3d7(3d6) 3(4) 3(4)
Ni2+ 3d8 2 2
Cu2+ (Cu+) 3d9(3d10) 1(0) 1(0)
 Types of Magnetism

Cooperative behavior
 Ferromagnetism
 Antiferromagnetism
 Ferrimagnetism
Non-cooperative (statistical) behavior
 Diamagnetism
 Paramagnetism
Diamagnetism:
 very weak , nonpermanent and persists only while an external field is being applied.
 Induced magnetic moment is extremely small, and in a direction opposite to that of
the applied field.
 Thus, r is less than unity (however, only very slightly), and the magnetic
susceptibility is negative.
Paramagnetism:
 a permanent dipole moment by virtue of
incomplete cancellation of electron spin and/or
orbital magnetic moments.
 the orientations of these atomic magnetic
moments are random, such that a piece of material
possesses no net macroscopic magnetization.
These atomic dipoles are free to rotate, and
paramagnetism results when they preferentially
align, by rotation, with an external field
Ferromagnetism:
• Certain metallic materials possess a permanent magnetic moment in the absence of
an external field,

• Manifest very large and permanent magnetizations.

• Permanent magnetic moments result uncancelled electron spins as a consequence of

the electron structure

• Coupling interactions cause net spin magnetic moments of adjacent atoms/ions to

align with one another, even in the absence of an external field.

• This mutual spin alignment exists over relatively large volume regions of the
crystal called domains

Bs =µoMs
Antiferromagnetism:
The alignment of the spin moments of neighboring atoms or ions in exactly
opposite directions is termed antiferromagnetism.

Nickel oxide (NiO) is one material that displays this behavior.

No net magnetic moment is associated with the O2- ions, since there is a total
cancellation of both spin and orbital moments.

However, the Ni2+ ions possess a net magnetic moment that is predominantly of
spin origin. These ions are arrayed in the crystal structure such that the moments of
adjacent ions are antiparallel.
Ferrimagnetism:
Antiparallel spin-coupling interactions, but not same magnitude. However, the net

ferrimagnetic moment arises from the incomplete cancellation of spin moments

 Theory of Magnetic Ordering
Exchange energy: Heisenberg model: E ex  2J ex Si  S j  2J ex SiS j cos 

 Si·Sj: spin angular momentum

 Jex:a numerical quantity called exchange integral

 Eex : is the exchange energy

Relative orientation of two spins determines the energy states.

1) If Jex is positive, Eex is a minimum when the spins are parallel (Cos  = 1), leading to
ferromagnetism

2) If Jex is negative, Eex is a minimum when the spins are antiparallel (Cos  = -1), leading to
antiferromagnetism.

Ferrites are special case of antiferromagnetism with net magnetic moment

• The reason behind domain formation

Domains form solely to minimize the

magnetostatic energy .

Once domains form, the orientation of dipole in

each domain and the domain size are determined
by magnetostatic, crystal anisotropy,
magnetoelastic, and domain wall energy.

All domain structure calculations involve

minimization of the appropriately selected
energies.
Initial magnetization Saturation magnetization
 What is Ferrites?
Magnetic ceramics or ferrites are a well established group of
magnetic materials and have appication in electronics, electronics
machines and materials. They exhibit certain common properties:

 They are all oxides

 They are based on Fe2O3 as a major compositional ingredient

 They exhibit a spontaneous magnetic induction in the absence of an

external magnetic field

 Existence of magnetic moment in ferrites materials arises due to

the presence of elements/cations with the partially filled inner
electronic shells . Each unpaired electron gives magnetic moment of
one Bohr magneton, 1B.
Why Ferrites are important magnetic materials?

 Strong magnetic coupling

 High resistivity
 Low magnetic loss characteristics
 Chemical stability
 Easy to manufacture(by powder metallurgy method)
 Classification of Ferrites
Structure Composition Application
Cubic General structure MeFe2O4, Soft magnets
Spinel Ferrites where Fe is trivalent and Me is
divalent Ni, Mn, Mg, Zn, Cu,
Co, Cd or a mixture.
1 Fe2O3 : 1 MeO
Cubic General structure R3Fe5O12, Microwave devices
Garnet Ferrites where Fe is trivalent and R is
Y or a trivalent rare earth,
typically Gd, Dy, Sm, Tb, Ho
etc.
3R2O3 : 5 Fe2O3
Magnetoplumbites Me Fe12O19 where Me is a Hard magnets
or diavalent Ba, Sr, Pb, Ca
Hexagonal Ferrites 1 MeO : 6 Fe2O3
BaFe12O19, SrFe12O19
PbFe12O19, CaFe12O19
 Spinel Ferrites
The natural mineral spinel MgO.Al2O3=MgAl2O4(AB2O4).Eight formula units make a unit cell
containing 56 atoms.The oldest spinel ferrite is magnetite which is a natural oxide.In spenil
there are Octahedral B- sites(32 sites) and Tetrahedral A-sites(64 sites).Lattice parameter ,a,
of spinel ferrites varies from 8.3 -8.7 Angstrom.
Metal Ions in the Unit Cell of Spinel Ferrite MeFe2O4
Kind of Size of Number Number Occupants
site site ( ) of of
available occupied Normal Inverse
sites sites spinel spinel
Tetrahed 0.5.5-
64 8 8Me2+ 8Fe3+
ral (A) 0.67
Octahed 8Fe3+
0.67-0.9 32 16 16Fe3+
ral (B) 8Me2+
 Types of spinel Ferrite
 Normal spinel ferrites: (Me2+)A[Fe3+Fe3+]BO4 :where Me =Zn, Cd (divalent)
example :ZnFe2O4 or (Zn2+)A [2Fe3+]BO4 & CdFe2O4 or (Cd2+)A [2Fe3+]BO4
They are nonmagnetic i.e. paramagnetic
 Inverse spinel Ferrites:(Fe3+)A[Me2+Fe3+]BO4 where Me= Fe, Ni, Co, Mg, and
Cu.
Example:Fe3O4 or (Fe3+)A[Fe2+Fe3+]BO4 , NiFe2O4 or (Fe3+)A[Ni2+Fe3+]BO4
3+ 2+ 3+ 3+ 2+ 3+
,CoFe2O4 or (Fe )A[Co Fe ]BO4, and CuFe2O4 or (Fe )A[Cu Fe ]BO4 .
They are all ferrimagnetic.
 Mixed or random spinel ferrites:(Me2+xFe3+1-x)A[Me2+1-xFe3+1+x]BO2-4
Example: ZnxNi1-x Fe2O4 or :(Zn2+xFe3+1-x)A[Ni2+1-xFe3+1+x]BO2-4 .
Magnetic moment of A –sites and B –sites are anti- parallel. Therefore
the resultant magnetic moment of a ferrite is :nB = MB – MA
• when x = 1; normal spinel
• when x = 0; inverse spinel
• when 0 < x < 1; mixed spinel ferrires.
The theoritical magnetic moment in Bohr magneton atT= 0 K ,can be calculated as,
nB = MB – MA
• The magnetization, Ms(emu/gm)per unit mass is given by the following formula

Molecular . weight  M s
nB 
N  B
• Where nB is the saturation magnetization per formula unit in Bohr magneton, Ms is
the saturation magnetization in emu/gm, N is the Avogadro’s number, 6.02×1023
and µB is the Bohr magneton, 0.927×10-20erg/Oe
 Theoretical magnetic moment calculation
Calculation of magnetic moment in Bohr magneton (nB) and saturation magnetization, Ms
(emu/gm using above equation) of Ni0.75Zn0.25Fe2O4,, Ni0.55Zn0.45Fe2O4 mixed ferrites are:

• Ni0.75Zn0.25Fe2O4 → [ Zn0.25Fe0.75]A [ Ni0.75Fe1.25]B O4

(0×0.25)+(5×0.75) (0.75×2)+(1.25×5)
= 3.75 µB = 7.75 µB
Net,
nB = (7.75 µB - 3.75 µB ) = 4 µB

• Ms (emu/gm) can be calculated using equation for the respective Ni-Zn ferrites are
When, Zn=0.25; or, n  Molecular . weight  M s
N  B
B

234.33 M s
4
6.02 1023  0.927 10 20

Ms= 95 emu/gm
Magnetic Behavior of Spinel ferrites Composition
Ferrite Postulated ion Distribution Magnetic Magnetic Magnetic Moment Magntizati Lattice const.
Moment (B) Moment (B) (B) per Molecule on (Å)
of of Octahedral MeFe2O4 emu/gm
Tetrahedral Ions at 0K
Ions
Tetrahedral Octahedral Theor Experi
Ions (A) Ions (B)

ZnFe2O4 Zn2+ 2Fe3+  0 0 0 0 0 8.44

CdFe2O4 Cd2+ 2Fe3+  0 0 0 0 0 8.70

0.8Mn2++ 0.2Mn2+ +
MnFe2O4 4+1 1+9 5 4.6 112 8.50
0.2Fe3+ 1.8Fe3+

Fe3O4 Fe3+ Fe2+ + Fe3+ 5 4+5 4 4.1 98 8.39

CoFe2O4 Fe3+ Co2+ + Fe3+ 5 3+5 3 3.7 90 8.38

NiFe2O4 Fe3+ Ni2+ + Fe3+ 5 2+5 2 2.3 56 8.34

CuFe2O4 Fe3+ Cu2+ + Fe3+ 5 1+5 1 1.3 30 8.37*

0.1Mg2+ 0.9Mg2+ +
MgFe2O4 0+4.5 0+5.5 1 1.1 31 8.36
0.9Fe3+ 1.1Fe3+

Li+0.5 +
Li0.5Fe2O4 Fe3+ 5 0+7.5 2.5 2.6 69 8.33
1.5Fe3+
 Yafet-Kittel (Y-K) angles
The decrease of magnetization can be treated theoretically by
triangular arrangement of spins as proposed by Yafet and Kittel.
Yafet-Kittel (Y-K) angles are calculated by using the formula,

n B  M B (x) cos  YK  M A ( x)
where Y-K is the canted angle (Y-K angle), MA and MB are the
magnetic moment of A and B sites. As the canting angle cos YK
increases, the value of magnetic moment on the B site (MB)
decreases, resulting in a decrease of overall magnetic moment
(nB) of the sample according to the above equation with
increasing Zn(x) or Cd(x) The canting angle starts to develop
sizeable value when x is greater than 0.4 due to weakening of JAB
exchange interaction.
Theoretical calculation of lattice constant of spinel ferrites:
a th 
8
3 3
r
A 
 R O   3 rB  R O 

where Ro is the radius of the oxygen ion (1.32 Å) and rAand rB are the ionic radii of tetrahedral
(A-site) and octahedral (B-site), respectively. The values of rA and rB will depend critically on
the cation distribution of the system. In order to calculate rA and rB, the following cation distribution
is proposed for the composition Cu1-xZnxFe2O4:

where the brackets ( ) and [ ] indicate the A-site and B-site respectively. The cation
distribution is based on the following:

Zn2xFe13x A Cu12xFe13x B O24

according to the cation distribution of Cu-Zn ferrites, the ionic radius of A-site (rA) and B-site
(rB) can be theoretically calculated using the following relations [2]:

rA  C AZn r Zn  2
 CAFe'r(Fe3 )
rB 
1
2

C BCu r (Cu 2 )  C BFe r ( Fe3 ) 
where r(Zn2+), r(Cu2+) and r(Fe3+) are ionic radii of Zn2+(0.83), Cu2+(0.76) and Fe3+(0.67)
respectively,
Using these formulae, the ionic radius of A-site (rA) and B-site (rB) were calculated and also
the calculated theoretical lattice parameter given in Table.
x Chemical A-site B-site (Å) (Å) ath (Å)
formulae
0.0 CuFe2O4 Fe  3
1
Cu
2
1 
Fe13 O42 0.67 0.715 8.491

0.1 Cu0.9Zn0.1Fe
Zn 2
0 .1 Fe03.9  Cu 2
0.9 
Fe13.1 O42 0.686 0.711 8.503
2O4

0.2 Cu0.8Zn0.2Fe Zn 2

Fe03.8  0.702 0.706 8.516
2O4
0 .2
Cu 2
0.8 Fe 3
1.2 O 2
4

0.3 Cu0.7Zn0.3Fe Zn 2

0. 3 Fe03.7  Cu 2
0.7 
Fe13.3 O42
0.718 0.702 8.528
2O4

0.4 Cu0.6Zn0.4Fe
Zn 2
0. 4 Fe03.6  Cu 2
0.6 
Fe13.4 O42
0.734 0.697 8.541
2O4

0.5 Cu0.5Zn0.5Fe
Zn 2
0. 5 Fe03.5  Cu 2

Fe13.5 O42
0.75 0.693 8.544
2O4
0.5

0.6 Cu0.4Zn0.6Fe Zn 2

0. 6 Fe03.4  Cu 2
0.4 
Fe13.6 O42
0.766 0.688 8.566
2O4
Hysteresis loop of Hard and Soft magnets
 Hard ferrite vs. Soft ferrite
Hard Ferrites Materials
Materials which retain their magnetism and are
difficult to demagnetize are called hard ferrite
materials.
These materials retain their magnetism even after
the removal of the applied magnetic field. Hence
these materials are used for making permanent
magnets. In permanent magnets the movement
of the domain wall is prevented. They are
prepared by heating the magnetic materials to
the required temperature and then quenching
them. Impurities increase the strength of hard
ferrite materials.
They have large hysteresis loss due to large
hysteresis loop.
Susceptibility and permeability are low.
Coercivity and retentivity values are large.
Magnetic energy stored is high.
They possess high value of BH product.
The eddy current loss is high.
Soft ferrites Materials
Soft ferrite materials are easy to magnetize and
demagnetize.
These materials are used for making temporary
magnets. The domain wall movement is easy.
Hence they are easy to magnetize. By annealing
the cold worked material, the dislocation density
is reduced and the domain wall movement is
made easier. Soft magnetic materials should not
possess any void and its structure should be
homogeneous so that the materials are not
affected by impurities.
They have low hysteresis loss due to small
hysteresis loop.
Susceptibility and permeability are high.
Coercivity and retentivity values are less.
Since they have low retentivity and coercivity,
they are not used for making permanent
magnets.
Magnetic energy stored is less.
The eddy current loss is less because of high
resistivity.
 Application of Soft Ferrites

Field of application Products Requirements Materials

Soft Ferrites

Motors
Power conversion Large MR
Generators
electrical - mechanical Small HC
Electromagnets
Low losses = small Fe based materials, e.g.
conductivity Fe + » (0,7 - 5)% Si
Power adaption (Power) Transformers Fe + » (35 - 50)% Co

Transformer
Linear M - H curve
("Überträger")

LF ("low" frequency; up Small conductivity Fe + » 36 % Fe/Ni/Co »

Signal transfer to » 100 kHz) 20/40/40

HF ("high" frequency up Very small conductivity

Ni - Zn ferrites
to » 100 kHz)

Magnetic field Large dM/dH for H » 0 Ni/Fe/Cu/Cr »

"Mu-metal"
screening ideally mr = 0 77/16/5/2
 Application of Hard Ferrites
Field of application Products Requirements Materials

Hard Ferrites

Loudspeaker Fe/Co/Ni/Al/Cu
Small generators »50/24/14/9/3
Permanent magnets Small motors Large HC (and MR) SmCo5
Sensors Sm2Co17
"NdFeB" (= Nd2Fe14B)

Video tape
Data storage analog
Audio tape Medium HC(and MR),
BaFe12O19 ,NiCo, CuNiFe,
hystereses loop as
Ferrite core memory CrO2
rectangular as possible
Drum Fe2O3

Hard disc, Floppy disc

Magnetic ferrite or
garnets (AB2O4, or
Data storage digital A3B5O12), e.g.
with A = Yttrium (or
Bubble memory Special domain structure mixtures of rare earth),
and B = mixtures of Sc,
Ga, Al
Most common:
Y3Fe5O12,Gd3Fe5O12