Synthesis of magnetic

materials with ferrite as

potential applicant

Dr. K. G. Rewatkar
Department of physics,
Dr. Ambedkar College,
Nagpur
 Basic Magnetic Quantities

Magnetic Induction or
Magnetic Flux Density B

F  q vB
Units: N C-1 m-1 s = Tesla (T) = Wb m-2
2006 : UNESCO Nikola Tesla Year
150th birth Anniversary of Nikola Tesla
 Ampere’s law in free space

 B.dl   0 i
i

0= permeability of free

space
B = 4  10-7 T m A-1
= 4  10-7 H m-1
Magnetic dipole moment m

m=iA

Units: A m2
Area=A

i
 Magnetization M of a solid

A solid may have internal magnetic dipole

moments due to electrons

Magnetic dipole moment per unit volume

of a solid is called magnetization
m
M
V
Units: A m2/m3 = A m-1
 Ampere’s law in a solid

 B.dl   i
0  B.dl   0 i   0  M.d l

 B  0M 
i
  0 .dl  i
 

B0
 H.dl  i
B  0 H  0M

H: magnetic field intensity Units: A m-1

In free space
B  0 H 1
Inside a solid

B  0 H  0M 3

B  H 2

 = permeability of solid, H m-1


r  relative permeability of solid,
0 dimensionless
 M  H 4
: magnetic susceptibility of the solid
dimensionless

Type of magnetic solid 

diamagnetic (universal) -10-5

superconductor -1
paramagnetic +10-3

ferromagnetic +103-105
Origin of permanent magnetic moments in
solids:
1. orbital magnetic moment of electrons
2. spin magnetic moment of electrons
3. spin magnetic moment of nucleus

We will consider only spin magnetic

moment of electrons
Bohr magneton B

The magnetic moment due to spin

of a single electron is called the
Bohr magneton B

B= 9.273 x 10-24 A m2

Net moment of two electrons of

opposite spins = 0
Unpaired electrons give rise to
Paramagnetism in alkali metals
Net magnetic moment

atom crystal
Na 3s1 1 B
Fe 3d64s2 4 B 2.2 B

Co 3d74s2 3 B 1.7 B
Ni 3d84s2 2 B 0.6 B
Example :
The saturation magnetization of bcc Fe is
1750 kA m-1. Determine the magnetic
moment per Fe atom in the crystal.

a = 2.87 Å V = a3 = 2.873x10-30

Magnetic moment per atom

1750x1000x2.873x10-30 =
2.068x10-23 A m2 =
B 2.2 =
 Ferromagnetic, ferrimagnetic and
antiferromagnetic materials
Due to quantum mechanical interaction the
magnetic moment of neighbouring atoms
are aligned parallel or antiparallel to each
other.

Ferro- Anti- Ferri-

magnetic ferromagnetic magnetic
ferromagnetic Fe, Co, Ni, Gd

Eexchange interaction= Eunmagnetized-Emagnetized

Element Ti Cr Mn Fe Co Ni
d atom 1.12 1.18 1.47 1.63 1.82 1.98
d 3d orbital
1.5-2.0

Heusler Alloys: Cu2MnSn, Cu2MnAl

Ferromagnetic alloys made of non-ferromagnetic elements
Thermal energy can randomize the spin

Tcurie
Ferromagnetic heat
Paramagnetic

Fe 1043 K Co 1400 K
Ni 631 K Gd 298 K
Cu2MnAl 710 K
Ferrimagnetic materials

Ferrites M 2 Fe23 O42

M2+: Fe2+, Zn2+, Ni2+,

Mg2+, Co2+, Ba2+, Mn2+
Ferrites M 2 Fe23 O42

Crystal structure: Inverse spinel

O2+ FCC packing

8 THV Fe3+ THV =

Tetrahedral
Antiferromagnetic coupling
4 O2+

4 OHV Fe3+ M2+

OHV = Octahedral

.Net moment due to M2+ ions only

If Fe is ferromagnetic with atomic
magnetic moments perfectly aligned
due to positive exchange interaction
then why do we have Fe which is not a
magnet?
Answer by
Pierre Ernest Weiss (1907)

Existence of domains known

as Weiss domains
Domain walls are regions of high energy
(0.002 Jm-2) due to moment misalignment.
Randomly aligned domains
1. decrease the manetostatic
energy in the field outside the magnet
2. increase the domain wall energy
inside the magnet

A magnet will attain a domain structure

which minimizes the overall energy
 B  0 H  0M

B never saturates
M saturates
The value of B at
the saturation of M
is called the
saturation
induction (~ 1 T)
Saturation induction

Two ways for

aligning of
magnetic
domains:
1.Growth of
favorably oriented
Initial permeability domains (initially)
2.Rotation of
domains (finally)
 The hysteresis
Loop

Br residual
induction

Hc coercive
field

Area =
hysteresis loss
Soft magnetic materials
For application requiring high frequency
reversal of direction of magnetization
Eg. Tape head

High initial permeability

Low hysteresis loss
Low eddy current losses
 Soft magnetic materials
For low hysteresis loss (  frequency)

Easily moving domain walls

Low impurity,
low non magnetic inclusions
low dislocation density
low second phase precipitate

For low eddy current loss (  frequency2)

Material: high resistivity

Design: Lamination

Choose: Pure, single phase, well-annealed material of high resistivity

Hard magnetic materials
For permanent magnets

Motors, headphones

High Br, high Hc

Br Hc = energy product

Mechanically hard c Magnetically hard

Martensitic high carbon steels (Br Hc=3.58 kJm3)

Alnico alloys: directionally solidified and annealed in a magnetic field (Br
Hc=5.85 kJm3)

Large M phase as elongated particle in low M matrix

Elongated Single Domain (ESD) magnets

Long particles, thickness < domain wall thickness

Each particle a single domain

No domain growth possible only rotation

Ferrite: BaFe12O19 (Br Hc=48-144 kJm3)

Co-Rare Earths (Sm, Pr) (Br Hc=200 kJm3)

Nd2 Fe14 B (Br Hc=400 kJm3)

The term “ferrite’ means different to
different scientists.

To metallurgists, ferrite means pure

iron. To geologists, ferrites are a group
of minerals based on iron oxide.

To an electrical engineer, ferrites are a

group of materials based on iron oxide,
but one that have particular useful
properties: magnetic and dielectric.
Magnetite or Lodestone is a naturally occurring iron oxide
that is considered a ferrite by both geologists and
engineers. Over 2,000 years ago, the Greeks recognized
the strange properties of Lodestone and almost 1000
years ago the Chinese used it to invent the magnetic
compass. Dielectric properties mean that even though
electromagnetic waves can pass through ferrites, they do
not readily conduct electricity. This gives them an
advantage over iron, nickel and other transition metals
that have magnetic properties (“ferromagnetic”) in many
applications because these metals also conduct
electricity.
Magnetite, i.e., Fe+2Fe+3O-4 (FeO,Fe2O3) is a
naturally occurring ferrite. The first artificial
ferrite was actually made in 1909 by Hilpert.
Scientific research on ferrite begun in the
mid - nineteenth century. Two Japanese
scientists Kato Yogoro and Takei Takeshi
(1932) took the initiative in conducting
serious research oriented to industrial
applications. Their series of research
results on Cu ferrite and Co ferrite in the
year beginning 1932 become the nucleus
and motive force which, as is well known
led to the world’s first application of ferrite
on a commercial basis.
ORIGIN OF MAGNETISM

Basically every materials is magnetic in nature, as

it possess charged particles which are in
continuous motion. Magnetism is present mainly
due to the motion of electrons.
eh

4mc

B = 9.27 x 10-21 erg/oersted

The magnetic interaction, which arises
because of the relative orientations of the
orbital and spin moments of various
electrons are as follows:
• The coupling of orbital motion of electrons
and spin momenta leads to Coulomb
interaction.
• Spin – orbit interactions, which magnetically
couple the orbital motion of each electron to
its own spin.
• Interactions produced because of electric
field of neighbouring ions of the crystalline
lattice.
CLASSIFICATION OF MAGNETIC MATERIALS
• Non – Cooperative phenomena
Where there is no collective magnetic interaction of
atomic magnetic moments with each other and are not
magnetically ordered.
ex: (i) Diamagnetic materials
(ii) Paramagnetic materials
• Cooperative phenomena
Where the magnetic dipoles interact with each other
introduces three types of behaviour, ex:
(i) Ferromagnetism
(ii) Antiferromagnetism
(iii) Ferrimagnetism.
 (a)Paramagnetic state
(b)Ferromagnetism
(c) Neel type
antiferromagnetism
(d) Neel type
ferrimagnetism
(e) Yafet – Kittel type
ferrimagnetism
(f) Helical spiral structures
(e) Canted spin weak
ferromagnets
(h) Canted spin compensated
antiferromagnets
(a) (b)

(c) (a) Diamagnetism

(b) Paramagnetism
(c) Ferromagnetism
(d) Antiferromagnetism
(e) Ferrimagnetism

(d) (e)
(a) (b)

(c)
(a)Diamagnetism
(b)Paramagnetism
(c)Antiferromagnetis
m
Hysteresis loop
 GENERAL PROPERTIES OF FERRITES

• Ferrites are generally black or grey in appearance.

Most ferrites are opaque. This can be attributed to
the approximately equal energies of the 3d and 4s
states. This is also because the absorption in case
of ferrites crystal structure occurs only in visible
range thus making them black by Waldron (1961). .
• Ferrites have high dielectric constant. Its values
are generally of the order of thousands at lower
frequencies, falling to about ten to twenty at
microwave frequencies. This is due to the close-
packed structure( hcp ) of oxygen ions .
 GENERAL PROPERTIES OF FERRITES

• Ferrites are very hard and brittle and have

high melting point. Again this is due to the fact
that oxygen ions have a close-packed spatial
formation, thus making the ionic bonds very
strong.
• The ferrites melting points are difficult to
measure because they lose oxygen at high
temperatures.
• Ferrites are non-conductors of electricity but
behave as semiconductors under the
influence of an applied electric field.
 Ferrites are best known for their

• magnetic properties.
Magnetic Anisotropy: - Most of the ferrites have
an ability to get completely magnetized along a
preferred axis on the application of magnetic field.

• Hysteresis and Permeability: - Ferrites have

either thin hysteresis loop or square loops. The
ferrites with this loop come under the class of soft
ferrites and finds applications in devices like
transformers and inductors. The other with square loop
are classified as hard ferrites which find applications in
memory devices
CLASSIFICATION OF FERRITES

Ferrites are usually classified as soft ferrites , moderate and hard

ferrites.
The distinguishing characteristic of the first group is high
permeability. Its flux – multiplying power made it suitable for their
job in machines and devices.

The terms “SOFT” has nothing to do with their physical properties

but refers to their magnetic characteristics. Soft ferrite dose not
retain significant magnetization whereas hard ferrite magnetization
is considered permanent. Soft ferrite is the general term to a class
of ceramic and electromagnetic materials.

Magnetically hard materials, on the other hand are made into

permanent magnets having high coercivity as it once magnetized
may be able to resist the demagnetizing action of stray fields
including its own.
 Magnetic oxides Ferrites
Normal
Spinels (soft) M-occupy A site
M+2Fe2+3O4 Fe occuoy B site
Cubic with 8 formula unit
Two sites tetrahedral (A) Inverse
& octahedral (B) site.
½ of Fe occupy B site
& ½ of Fe occupy A site
M occupy B site

Random
Garandnet (moderate) M & Fe occupy A & B
Y3+3Fe5+3O12 site
BCC in cubic with 8 formula unit
Having three sites Tetrahedral Hexaferrites (hard)
Octahedral Fe+3 ions occupy M+2Fe12+3O19
tetrahedral & octahedral sites in 2:3 ratio, Hexageonal with 2 formula unit
while Y+3 ions occupy dodecahedral sites
 Spinel structure A B2 O4

oxygen

B atoms in octa
hedral positions
A atoms in tetra
only front half of the cube is
shown
each B atom has 6 oxygen n.n. B – O – A paths:
each having just 1 A atom n.n.
6 starting from B
each A atom has 4 oxygen n.n.
each having 3 B atoms n.n. A – O – B paths:
12 starting from
A
46
 Co ferrite – distribution of cations over A and B sites
inverse normal

Fe3+ Co2+Fe3+ O2-4 Co2+ Fe3+ Fe3+ O2-4

tetra octa tetra octa

- - f.c.c. - - f.c.c.
hedral hedral
“frame” “frame”
positions positions
5μB 3μB 5μB 3μB 5μB 5μB

with magnetic with magnetic

moments moments
mixed with i = degree of inversion

Co2+1-i Co2+i M = MB-MA =[3i+5(2-i)]-(5i+3-3i) =

Fe3+i Fe3+2-i
=[10-2i] – (3+2i) = {7 – 4i} [μB]
Garnet Ferrites
These are the ferrites that can accommodate large
trivalent rare earth ions with large magnetic moments.
Garnet ferrites have the structure of the silicate mineral
garnet. Magnetic garnets crystallize in the dodecahedral
or 12-sided structure related to the mineral garnet. The
general formula is 3Me2O3.5Fe2O3 or Me3Fe5O12. It is to be
noted that in this case all the metal ions are trivalent in
contrast to the other two classes. In the important
magnetic garnets, Me is usually Yttrium (Y) or one of the
rare earth ions.

The general formula of the garnets can be represented

schematically by {C3}[A2](D3)O12 where the cations are
subdivided into three main sites with different coordinates.
The cation C has dodecahedral, A octahedral and D
tetrahedral coordination.
Naturally occurring magnetite is a weak
‘hard’ ferrite.
Hard ferrites possess magnetism, which is
essentially permanent. Man made hard
ferrites with superior properties were
developed but producing an analogous ‘soft’
magnetic material in the laboratory proved
elusive.
In the case of hard ferrites, a strong
magnetization remains after a magnetizing
field has been removed and residual
magnetization is stable even if certain strength
of demagnetizing field is applied.
The best known compounds in this
class are,

BaFe12O19,
SrFe12O19,
CaFe12O19 ,
PbFe12O19.
 Chemical composition of hexagonal compounds in BaO-MeO-Fe2O3 systems
M and Other related hexagonal ferrites

Symbol Crystallographic Number of Chemical Formula Composi

building up per molecules tion
unit cell per unit cell ( mol % )

MeO BaO Fe2O3

S MeO.Fe2O3 MeFe2O4 50 - 50
T MeO.2Fe2O3 BaFe4O7 - 33.33 66.67
B Bao.Fe2O3 BaFe2O4 - 50 50

M RSR*S* 2M BaO.6Fe2O3 BaFe12O19 - 14.29 85.71

W RSSR*S*S* 2MeW 2MeO.BaO.8Fe2O3 Me2BaFe16O27 18.18 9.09 72.71
Y 3 ( ST ) 3MeY 2MeO.2BaO.6Fe2O3 Me2Ba2Fe12O22 20 20 60
Z RSTSR*S*T*S* 2MeZ 2MeO.3BaO.12Fe2O3 Me2Ba2Fe24O41 11.76 17.65 70.59
X 3( RSR*S*S* ) 3MeX 11.11 11.11 77.78
2MeO.2BaO.14Fe2O3 Me2Ba2Fe28O48
U RSR*S*T*S* MeU 8.33 16.67 75.00
2MeO.4BaO.18Fe2O3 Me2BaO4Fe36O60

*180 degree rotational symmetry around the hexagonal c-axis

 Various types of Hexagonal Ferrites

Chemical Symbol* Structural Units No. of Oxygen Lattice

Composition (Blocks)* Layers Parameter (c)
(Å)
BaFe12O19 M RSR’S’ 2 x 5 = 10 23.19

Ba2Me2Fe12O22 Y (TS)3 3 x 6 = 18 43.6

BaMe2Fe16O27 W RS2R’S2’ 2 x 7 = 14 32.8

Ba3Me2Fe24O41 Z RSTSR’S’T’S’ 2 x 11 = 22 52.3

Ba2Me2Fe28O46 X (RS2R’S2’)3 3 x 12 = 36 84.1

Ba4Me2Fe36O60 U (RSR’S’TS’)3 3 x 16 = 48 113

* The blocks with prime signs are related to the unprimed blocks by a 180o
rotation about the c-axis.
The composition diagram of hexagonal ferrites
Fe2O3
100 0
M = BaFe12O19
M
W = BaMe2Fe16O27
Z = Ba3Me2Fe24O41
80 20
Y = Ba2Me2Fe12O22
Z W
S = Ba2Me2Fe28O46
60 40
Y

BaFe2O4 SX
The symbol Me
40 60 represent a divalent
ion or a combination
of divalent ions.
20 80

100
0
BaO 20 0 MeO
100 80 60 40
Perspective
illustration
of unit cell
of
PbFe12O19
The sequence
of layer in
BaFe12O19
Coordination number and direction of magnetic moment of
Fe3+ ions in the unit cell of the magnetoplumbite type crystal.

Coordination number Number of Wyckof’s Direction of magnetic Remarks

Positions notation moment per mole

6 12 k ↑↑↑↑↑↑ I (a)

(Octahedral site) 4 f2 ↓↓ III (d)

2 a ↑ V (b)

4 4 f1 ↓↓ II (c )

(Tetrahedral site)

5 2 b ↑ IV (e)

(Trigonal bipyramidal site)

Three types of locations in M structure
Exchange interaction scheme in the unit cell of M structure
(110) plane of the hexagonal structure of BaFe12O19. The strong
lines indicate the most important exchange interactions between
the five iron sublattices.
Known compounds of substituted M-type compounds with Al, Ga, Cr, La etc.

Formula a (Å) c (Å) Ref.

BaAl12O19 5.577 22.67 Adelskold (1938)
5.66 22.285 Bertaut et al. (1959)
SrAl12O19 5.557 21.945 Adelskold (1938)

CaAl12O19 5.566 22.010 Wisnyi (1967)

Ca(AlFe)12O19 5.792±0.004 22.56±0.04 MacChesney et al.(1971)

BaGa12O19 5.818 23.00 Bertaut et al. (1959)

5.850±0.004 23.77±0.02 Verstegen (1973)
SrGa12O19 5.796±0.004 23.77±0.02 Verstegen (1973)

LaMgGa11O19 5.799±0.003 22.71±0.01 Verstegen (1973)

BaCr8Fe4O19 5.844 22.82 Bertaut et al. (1959)

SrCr6Fe6O19 5.844 22.77 Bertaut et al. (1959)

CaFe11Ir0.5Co0.5O19 5.6952 22.8135 B. Sugg et al (1995)

CaFe10IrCoO19 5.8239 22.9256 B. Sugg et al (1995)

CaFe12O19 5.877 22.910 B.T. Borkar (1987)

 Applications of materials

Permanent magnet Magnetic Recording Computer Microwave Radio and Television Telecommunication Miscellaneous uses

Motors Erase heads Pulse Transformer Cores

Antenna Cores Delay Line Impedar Ferrite Powder
Type Tittles Cores Cores For Copying
machine
Loud Speakers Magnetos Memory Substrates for
Fly back Deflection Electrolytic
Cores Bubble Memories
Transformer Cores Electrodes
Rubber Magnet Yoke Cores
Reactor
Cores Electromagnetic
IFT Cores Rotary Cores
Audio Tapes Magnetic diskette
Power Transformers Transformer Cores
Magnetostrictive
Computer Tapes
Vibrators
Ferrite Microwave Rubber
Low Accommodation Low Temperature
Ferrites
Video Tapes Magnetic Cards Absorber Coefficient Cores
Cores

Noise Absorber Isolators Circulator Low Loss Cores High Stability Cores
Core
Magnetic Recording Heads
Aplication of Magnetic Ceramics

Entertainment electronic (Radio, TV)

Computer
Microwave applications (Radar,
communication, heating)
Recording Tape
Permanent motor
Aplication of Magnetic Ceramic ferrites.

 Spinel (cubic ferrites): Soft magnets

 Garnet (rare earth ferrites): Microwave devices

 Magnetoplumbite (hexagonal ferrites): Hard magnets

Aplication of Soft Magnetics
 In the soft magnetic materials, only a small
field is necessary to cause demagnetization and
very small energy losses occur per cycle of
hysteresis loop.

 This is important for applications such as

transformers used in touch tone telephones or
inductors or magnetic memory cores.

 Duringused a soft ferrites has its magnetic

domains rapidly and easily realigned by the
changing magnetic field.
 Aplication of Hard Magnetics
A hard (or permanent) ceramic magnet achieves its
magnetization during manufacture.

 The magnetic domains are “frozen in” by poling in an

applied magnetic field as the material is cooled through
its Tc.

 The materials are magnetically very hard and will retain

in service the residual flux density, that remains after the
strong magnetizing field has been removed.

 Hard ferrites are used in loudspeakers, motors.

 Aplication of Ferrites
 The cubic spinels, also called ferrospinels, are used as
soft magnetic materials because of their very low
coercive force of 4x10-5 weber/m2 and high saturation
magnetization 0.3-0.4 weber/m2.
(1 weber = 1 volt-second = 108 Maxwells)
 Flux density (induction): 1 Tesla = 104 Gauss = 1
weber/m2. (1 Gauss = 1 Maxwell/cm2).
 Hexagonal ferrites are hard magnetic materials with
coercive force of 0.2 – 0.4 weber/m2 and large resistance
to demagnetization, 2 – 3 J/m3.
Aplication of Garnets
 Garnets are especially suited for high
frequency microwave applications due to
the ability to tailor properties such as
magnetization, line width, g-factor, T c, and
temperature stability.

 Themost common garnet ferrites are based

upon
3Y2O3 : 5Fe2O3 or Y3Fe5O12 or YIG.
 Tape Recording
 Before passing over the record head,
a tape passes over the erase head
which applies a high amplitude, high
frequency magnetic field to the tape
to erase any previously recorded
signal and to thoroughly randomize
the magnetization of the magnetic
emulsion.
 The gap in the erase head is wider
than those in the record head; the
tape stays in the field of the head
longer to thoroughly erase any
previously recorded signal.
 Tape Recording
 High fidelity tape recording requires a high frequency
biasing signal to be applied to the tape head along with
the signal to "stir" the magnetization of the tape .
 This is because magnetic tapes are very sensitive to their
previous magnetic history, a property called hysteresis.
 A magnetic "image" of a sound signal can be stored on
tape in the form of magnetized iron oxide or chromium
dioxide granules in a magnetic emulsion.
 The tiny granules are fixed on a polyester film base, but
the direction and extent of their magnetization can be
changed to record an input signal from a tape head.
Electromagnet
 Electromagnets are usually in the form of iron
core solenoids.
 The ferromagnetic property of the iron core
causes the internal magnetic domains of the
iron to line up with the smaller driving
magnetic field driving produced by the current
in the solenoid.
 The solenoid field relationship is

and k is the relative permeability of the iron,

shows the magnifying effect of the iron core.
Transformer
A transformer makes use of Faraday’s law and the
ferromagnetic properties of an iron core to efficiently
raise or lower AC voltages.
 It of course cannot increase power so that if the voltage
is raised, the current is proportionally lowered and vice
versa.
Transformer
 Applications of GMR
 The largest technological application of GMR is in the data
storage industry.
 IBM were first to market with hard disks based on GMR
technology although today all disk drives make use of this
technology.
 On-chip GMR sensors are available commercially from
Non-Volatile Electronics.
 It is expected that the GMR effect will allow disk drive
manufacturers to continue increasing density at least until
disk capacity reaches 10 Gb per square inch.
 At this density, 120 billion bits could be stored on a typical
3.5-inch disk drive, or the equivalent of about a thousand
30-volume encyclopedias.
Applications of GMR
 GMR also may spur the replacement of RAM in
computers with magnetic RAM (MRAM).
 Using GMR, it may be possible to make thin-film
MRAM that would be just as fast, dense, and
inexpensive.
 It would have the additional advantages of being
nonvolatile and radiation-resistant.
 Data would not be lost if the power failed
unexpectedly, and the device would continue to
function in the presence of ionizing radiation, making
it useful for space and defense applications.
 Other applications are as diverse as solid-state compasses,
automotive sensors, non-volatile magnetic memory and
the detection of landmines.
Applications of GMR

 Reading and writing with a magnetoresistive probe.

 C B Craus, T Onoue, K Ramstock,W G M A Geerts, M H Siekman, L Abelmann
and J C Lodder, J. Phys. D: Appl. Phys. 38 (2005) 363–370
The preparation techniques
reported for ferrites are-
 Solid state method
 Co-precipitation
 Aerosol pyrolysis
 Hydrothermal synthesis
 Glass crystallization
 Microemulsion
 Dry milling method
 sol gel combustion route
Many plus of sol gel combustion
route-

* energy efficient
* short reaction rate
* ultra fine powder of nano particles
* facile operation
* low anneal or calcine temperature
* better particle size distribution
* excellent chemical homogeneity
* more probability of formation of single domain
structure
Experimental details ….
A series of samples were prepared of
chemical formula Ca/Sr/BaFe12-xMxO19

 A yellow–green-brown transparent
aqueous solution of metal nitrates or
chlorates, nitric acid and fuel as citric
acid, urea and ethylene glycol was
prepared.

 It is important to note the mole ratio of

citric acid to metals ions in solution.

 The solution was heated under constant

stirring at a temperature of about 100–150
oC in a Pyrex beaker, produced brown gel.
PREPARATION OF SAMPLE BY SOL GEL ROUTE ….
PREPARATION OF SAMPLE BY SOL GEL ROUTE ….
PREPARATION OF SAMPLE BY SOL GEL ROUTE ….
The resulting brown/black were ground in an agate
mortar, put into alumina crucibles, and then calcined
at 150 oC for 1 h.
The powders and 10% polyvinyl
alcohol solution (5–6 drops) had
been mixed before they were
pressed into pellets of 10 mm in
diameter and about 5 mm in
thickness.

The pellets of each composition

which were then sintered at
800 oC for 4 h in air.
 Experimental details ….

• Crystallographic structures were examined by powder X- ray

diffraction (XRD). Morphology and grain size can be
determined with SEM and TEM.

• Hysteresis measurements/ Magnetic studies can be carried out

on magnetic hysteresis recorder .

• Room temperature Mossbauer spectra were recorded using a

constant acceleration spectrometer. (γ-ray source was 50mCi
57
Co in Rh matrix)

• Morphology and grain size were taken with Scanning electron

microscope. SEM and TEM studies reveals the nano-scale
crystalline structure of the compounds under study.
XRD pattern of CaFe12-xCrxO19
Variation of
lattice (a and c)
parameters with
Cr content
CaFe12-xCrxO19
with x = 0.0 - 0.8.
Lattice parameter of some substituted M-type compounds with Al, Ga, Cr, La
etc.
Formula a (Å) c (Å) Ref.
BaAl12O19 5.577 22.67 Adelskold (1938)
5.66 22.285 Bertaut et al. (1959)
SrAl12O19 5.557 21.945 Adelskold (1938)

CaAl12O19 5.566 22.010 Wisnyi (1967)

Ca(AlFe)12O19 5.792±0.004 22.56±0.04 MacChesney et al.(1971)

BaGa12O19 5.818 23.00 Bertaut et al. (1959)

5.850±0.004 23.77±0.02 Verstegen (1973)
SrGa12O19 5.796±0.004 23.77±0.02 Verstegen (1973)

LaMgGa11O19 5.799±0.003 22.71±0.01 Verstegen (1973)

BaCr8Fe4O19 5.844 22.82 Bertaut et al. (1959)

SrCr6Fe6O19 5.844 22.77 Bertaut et al. (1959)

CaFe11Ir0.5Co0.5O19 5.6952 22.8135 B. Sugg et al (1995)

CaFe10IrCoO19 5.8239 22.9256 B. Sugg et al (1995)

CaFe12O19 5.877 22.910 B.T. Borkar (1987)

Effect of annealing temperature on the particle size ….
 100 nm

(a) (b)

(c) (d)

SEM of CaFe12-xCrxO19 for (a) = 0, (b) = 0.2, (c) = 0.4, (d) = 0.6
Influence of heat treatment on the magnetic Magnetic properties of
properties(Hc, Ms) of Sr(ZnTi)0.5Fe11.2O19 Sr(ZnIr)xFe12-xO19 vs. ‘a’
substitution content x
Effect of the pH on the phase formation,
crystalline size and magnetic properties of
strontium hexaferrite powders for Fe+3/Sr+2 ratio
10 and annealed at 1ooo0C for 2h.
Effect of Fe+3/Sr+2 mole ratio on M-H hysteresis loop of
synthesized SrFe12O19 powders obtained annealed at 10000C
for time 2h through co-precipitation route at pH 10 .
Saturation magnetizations of the Coercivity of CaFe12-xCrxO19 pellets with
CaFe12-xCrxO19 pellets with x= 0 – 0.8 x= 0 – 0.8
Room temperature hysteresis of CaFe12-xCrxO19
Fitted room temperature MÖssbauer spectrum of CaFe11.6Cr0.4O19
Hyperfine fields at each crystallographic site of CaFe 12-xCrxO19 ceramics with x= 0 – 0.8
Relative areas on each crystallographic site of CaFe12-xCrxO19 ceramics with x= 0 – 0.8
Conclusions
 Preheating the gel between 400oC and 500oC for several hours
is a key step. It can prevent the formation of intermediate
α-Fe2O3 and obtain strontium ferrite single phase with
narrow size distribution at a low heating temperature.
 Saturation magnetization and coercive field strength are
determined depending on the heat treatment of the gel and the
ratio of iron and strontium in the starting solution.
 The crystal growth can be easily controlled by varying the
heat treatment in order to prepare nanocrystalline
hexaferrite particles with single domain behavior and a narrow size
distribution of about 7–100 nm.
 The substituted ferrite can also possess hexagonal
structure. It possesses excellent microwave absorption property with
the maximum absorption efficiency of 34.76 dB.
 Aluminum substitution makes the ferromagnetic resonant
frequency of barium ferrite to increase to 14.56 GHz, while the
chromium substitution decreases it.
Conclusions
 The multi-peak phenomenon arises during the
ferromagnetic resonance, which is mostly resulting from the
spin wave instability.
 The lattice constants a = 5:8925 Å, c = 23:11223 Å are
slightly influenced by chemical composition and the annealed
temperatures, but independent of R value.
 TEM observation of as-burnt powders of Ba(MnTi)Fe10O19
indicates that the powder particles have an average diameter
of 50 nm.
 Total substitution of Fe(III) by Co(II) and Ti(IV) leads to a
highly diluted magnetic material, BaCo6Ti6O19, having a very
weak magnetic moment. As the ratio of the Co(II)–Ti(IV)
substitution increases, the saturation magnetisation
decreases from substitution of x = 1 to 6, in the system of
BaCoxTixFe12−2xO19.
Conclusions
 The phase of Co(II)–Ti(IV)-substituted barium ferrite is found
to be crystallised on the (1 1 1) planes of spinel- structured iron
oxide, where the micrograph shows the distinctive angle of 70◦
between the two phases.
 A strontium surplus is important to synthesize single phase
SrFe12O19 by chemical co-precipitation method. Pure ultrafine
SrFe12O19 powders (98–159 nm) were obtained from precursors
with Fe3+/Sr2+ mole ratio of 9.23 after annealing temperature
from 900–1100 0C for 2 h in static air atmosphere.
 Increasing the pH for the precipitated precursors from 10 to 11.5
at Fe3+/Sr2+ mole ratio of 10 increased the formation of single-
phase SrFe12O19.
 The synthesis conditions were strongly influenced on the
microstructure of the produced Sr–M ferrite powders.
 The formed ultrafine pure SrFe12O19 powders had good magnetic
saturations (64.72–84.15 emu/g) and wide intrinsic coercivities
(2937–5607 Oe).
Conclusions
 The saturation magnetizations are closely related to
the distribution and concentration of Cr3+ ions on
the five crystallographic sites.
 Magnetic and Mossbauer results show that Cr3+ ions
preferentially occupy the octahedral 2a, 4fVI, and
12k sites.
 With Cr entering the Fe crystallographic sites, the
saturation magnetization dramatically falls but
the coercivity increases.
 The decrease in magnetization is therefore
attributed to Cr3+ ions occupying on the spin up Fe
sites (2a and 12k sites) and magnetic dilution or non-
collinear structure.
 It is evident that the Fe3+–O–Fe3+ super-exchange
interaction may be weakened by Cr3+(3d3)
substituting into some Fe(3d5) sites.
 Thank you
for your attention