Introduction to Ferrite

Nanoparticles
• Nanoparticles are those particles that are less than
100 nm in size .
• Nanotechnology is considered to be one of the most
important future technologies involving several
discipline of science including; solid state physics,
solid state chemistry, materials engineering, medical
science and biotechnology.
• The transition from bulk to nanoscale leads to a number of
changes in structural, physical, magnetic and electrical
properties.
• Due to high DC electrical resistivity and low dielectric
losses, nanoparticles are potential candidates as high
frequency electromagnetic wave absorbers.
• High transition temperature (ferrimagnetic to
paramagnetic) makes them ideal for high temperature
applications.
Ferrite nano materials are chosen due to their high (>106
-cm) DC electrical resistivity, good magnetic properties,
chemically stable over wide temperature range and low
eddy current losses. They have potential applications in:
• Electromagnetic absorbers
• Data storage
• Microwave devices
• Core Material
• Drug delivery
• Ferrites are iron containing complex oxide with interesting
magnetic and electrical properties and have been studied
extensively because of their important in basic as well as in
applied research.
• The DC electrical resistivity of ferrites can vary at room
temperature from 10-2Ω-cm to 1011 Ω-cm.
• The knowledge of cations distribution and spin alignment is
essential to understand the magnetic and electrical
properties of spinel ferrites.
Ferrites can be classified into three different types
• Spinel ferrites (MFe2O4)
• Hexagonal ferrites (MFe12O19),
• Garnets (Me3Fe5O12)
In spinel structure, cations rest on two types of interstitial
sites to preserve the charge neutrality namely tetrahedral
and octahedral sites.
• In a tetrahedral site the interstitial atom is in the
center of a tetrahedral arrangement of four oxygen
atoms at the lattice positions.
• Three of them, touching each other, are in plane; the
fourth atom sits in the symmetrical position on top
as shown in Fig. 1.
• There are 64 tetrahedral sites in a spinel structure.
• Out of which 1/8 are occupied by the cations.

Fig. 1. Tetrahedral sites in unit cell.

• An octahedral position for an interstitial atom is the
space in the interstices between 6 regular oxygen
atoms at the face-centered positions forming an
octahedral arrangement.
• Four regular atoms are positioned in a plane; the other
two are in asymmetrical position just above or below as
shown in Fig. 2.
• There are 32 octahedral sites in a spinel structure.
• Out of which 1/2 are occupied by the cations.

Octahedral
Fig. 2. Octahedral sites in unit cell.
 • The spinel ferrites have been further classified into three
categories due to the distribution of cations on tetrahedral
(A-sites) and octahedral (B-sites)
Types of spinel ferrites
• Normal spinel ferrites
o [(De2+) [D3+] O ]
A B 4 Ferrimagnetic spinel
• Inverse spinel ferrites
o [(D3+) [De2+D3+] O ]
A B 4
• Intermediate spinel ferrites
o [ (De 2+ D 3+) [De 2+ D 3+] O ]
δ 1- δ A 1-δ 1+ δ B 4
 Classification of magnetic
materials

• Diamagnetism
• Paramagnetism
• Ferromagnetism
• Antferromagnetsim
• Ferrimagnetism
 Diamagnetism
• The diamagnetic materials do not have any unpaired
electrons. So there are no net magnetic moments.
• In response to an external applied fields, diamagnetic
material produces a weak magnetization that opposes
the applied field giving rise to a negative susceptibility.
Examples; Gold, Copper, mercury, zinc
Paramagnetic

• Each atom
possesses a
permanent magnetic
moment.
• When H=0, all the
magnetic moment
randomly oriented,
so M=o
Paramagnetic
• When magnetic field
is applied the
magnetic moments
tend to orient
themselves in the
direction of the field.
• This result net
magnetization and
positive susceptibility
• Example; Al, Cr, Zr
Ferromagnetism
• Materials that retain a
magnetization in zero
field

• Magnetic moment are

parallel alignment in the
absence of an external
magnetic field

• Examples: iron, cobalt

Ferromagnetism

• Thermal energy can be

used to overcome
exchange interactions
• Curie temp is a measure of
exchange interaction
strength
Antiferromagnetism
• In some materials,
exchange interactions
favour antiparallel
alignment of atomic
magnetic moments
• Materials are
magnetically ordered
but have zero remnant
magnetization and very
low 
• Many metal oxides are
antiferromagnetic MnO
• CoO, MnS
Antiferromagnetism
• Thermal energy can
be used to overcome
exchange
interactions

• Magnetic order is
broken down at the
Néel temperature
(c.f. Curie temp)
Ferrimagnetism
• Antiferromagnetic
exchange interactions
• Different sized
moments on each
sublattice
• Results in net
magnetization
• Example: magnetite,
maghemite
Magnetic domains

• Ferromagnetic
materials tend to form
magnetic domains
• Domain; The small
region within which
single direction of
orientation of magnetic
moment.
• Each domain is
magnetized in a
different direction
Magnetic domains
• Applying a field
changes domain
structure
• Domains with
magnetization in
direction of field
grow
• Other domains
shrink
Magnetic domains

• Applying very strong

fields can saturate
magnetization by
creating single
domain
Magnetic domains
• Removing the field
does not necessarily
return domain
structure to original
state

• Hence results in
magnetic hysteresis
 Magnetic susceptibility, 
• Magnetic susceptibility is sometimes
written as

• And sometimes as the slope of M vs H

 How does M respond to H?
• There is a variety of ways that M responds to H
• Response depends on type of material
• Response depends on temperature
• Response can sometimes depend on the previous
history of magnetic field strengths and directions
applied to the material
Non-linear responses
• Generally, the
response of M to H
is non-linear
• Only at small values
of H or high
temperatures is
response sometimes
linear

• M tends to saturate
at high fields and low
temperatures
Low field magnetic susceptibility

• For some materials,

low field magnetic
susceptibility is
inversely
proportional to
temperature

• Curie’s Law
A high temperature AC magnetic susceptometer probe was fabricated, based
upon the principle of mutual inductance. The instruments used for the
construction of this apparatus include;
• Pick-up coils (primary and secondary)
• Heating element
• DC power supply (up to 30 Amp)
• A thick glass tube (8 mm)
• An exhaust fan
• A DC adapter (12 V)
• Pt-100 temperature sensor (up to 800 0C)
• Lock-in amplifier
• Multi-meters
• A wooden stand

Fig. 4: Block diagram representing the high temperature AC magnetic

susceptibility measuring apparatus
• It was mandatory to calibrate the apparatus, which was newly
developed and to make it more and more precise.
• The transition temperature for pure
Ni measurement is found
to be 633 ± 5 K.
• That has an excellent
agreement with the
reported value 631±2 K
[Charles Kittle] for pure Ni.

Fig. 5. Variation of inverse AC magnetic susceptibility with

temperature for pure Ni.
Magnetic hysteresis
• Ferromagnetic material
normally does not possesses
net magnetization.
• For external magnetic field,
magnetic domains grows in
size thus the material get a net
magnetization.
• At certain magnetic field,
magnetization reaches a max
value.
Magnetic hysteresis

• M depends on previous
state of magnetization
• Remnant magnetization Mr
remains when applied field
is removed
• Need to apply a field
(coercive field) in opposite
direction to reduce M to
zero.
Effect of temperature on remnant
magnetization

• Heating a
magnetized material
generally decreases
its magnetization.
• Remnant
magnetization is
reduced to zero
above Curie
temperature Tc
Effect of temperature on remnant
magnetization
• Heating a sample
above its Curie
temperature is a way
of demagnetizing it

• Thermal
demagnetization
1. SolidState reaction Method
2. Wet Chemical Methods
• co-precipitation Method
• Sol-Gel Method
• Microemulsion Method
• Hydrothermal Method
• Solid State reaction Method
• Disadvantages
o High temperature (>1100 0C) and long sintering times for
reaction to complete
o Slow reaction rate
o Low homogeneity
o Larger particle sizes (>100 nm)
Advantages
• Low sintering temperatures are required
• Short sintering time
• High degree of homogeneous (mixing at atomic
level)
• High reaction rate
• Smaller particle size (<100 nm)
Disadvantages
The method does not work well when:
• When the reactants have different solubility in water
• The reactants don’t precipitate at the same rate
In order to use co-precipitation as the synthesis route the following
factors must be consider :
• Rate of Mixing of Reagents:
• The rate of mixing of reagents plays a vital role in the size of the resultant
particles.
• Co-precipitation consists of two processes: nucleation (formation of
centers of crystallization) and a subsequent growth of particles.
• Less dispersed in size colloid is formed when the rate of nucleation is high
and the rate of particles growth is low.
• To obtain ferrite particles of a smaller size, less dispersed in size and
more chemically homogeneous, the mixing of reagents must be
performed as fast as possible.
• Influence of Concentration of Reagents:
• Concentration of 0.1 to 0.2 mol/ is usually taken for the synthesis of
ferrite particles, .
• This allows to obtain non-viscous primary suspension of particles that is
important for better mixing of the reacting volume.
• At higher concentration (Me>0.4mol/ ) suspension becomes viscous,
and it is difficult to provide an intensive stirring.
Influence of Temperature:
• An increase in temperature in the range 20-1000C significantly
accelerates formation of ferrite particles.
• The activation energy for the formation of ferrites of different metals is
not equal.
Activation energy calculated from kinetics of the formation reaction for three different
ferrites in the temperature range of 20-1000C decreases in the following sequence
EA(Ni-ferrite) > EA(Co-ferrite) > EA(Zn-ferrite).
This sequence is also inagreement with the decreasing of dehydration temperature of
the individual hydroxides of the corresponding metals.
Influence of pH of the Reaction:
For the formation of ferrite, the yield of ferrite grows when the pH of the reaction is
increased from 6.8 to 8.6 followed by a slight increase.
The most interesting fact is that a further increase of pH up to 12. -14 leads to a
significant growth of the yield.
At high pH values the time of formation of ferrites become very short.
 Duration of Heating after Co-precipitation:
Co-precipitation takes place in a concentrated system,
but no information is given on growing of particles size,
which may occur in such a system during long heating
process. In our case, we heated the precipitates for 30
min.
• The precipitates formed in a state which is easily
filtered
 • At first solid hydroxides of metals in the form of colloidal particles
are obtained by the co-precipitation of metal cations in alkaline medium.
• For the case of Co-Ni ferrites this reaction is :
(1-x)CoCl2. 6H2O + xNiCl2 . 6H2O + 2Fe(NO2)3 .9H2O +8NaOH
(1-x)Co(OH)2.xNi(OH)2.2Fe(OH)3 +2NaCl+6NaNO3

• Then this product is subjected to heating in the precipitation alkaline

solution to provide the transformation of metal hydroxides solution to
the Co-Ni ferrites,

(1-x)Co(OH)2.xNi(OH)2.2Fe(OH)3 +2NaCl+6NaNO3
Co(1-x)NixFe2O4.nH2O + (4-n)H2O

where n is an integer.