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Introduction to Magnetic ceramics

Magnetic ceramics or ferrites are a well established group of


magnetic materials resulting from the rigorous research activities for
the last 50 years. Magnetic ceramic has virtually applications in
almost all areas of potential technologies. In some cases, there is no
other practical alternative materials. Magnetic ceramics or ferrites
cover a wide range of crystal structures, compositions and
applications. However 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 ceramic magnetic materials
is due to the presence of elements/cations with the partially
filled inner electronic shells such as Fe2+, Ni2+, Co2+, Mn2+.
Table below shows the electronics configurations and
unpaired electrons for many cations commonly found in
magnetic ceramics that give rise to net magnetic moment
within the structure. This is to note that each unpaired electron
gives magnetic moment of one Bohr magneton, 1B.
The important properties that make these materials useful are:
 Strong magnetic coupling
 High resistivity
 Low magnetic loss characteristics
 Chemical stability
Magnetic ceramics or ferrites are classified under Ferrimagnetism.
Ferrimagentism is a special case of enti-ferromagnetism in which
the magnitude of magnetic moment in one direction is different
from that of opposite direction resulting in a net magnetic moment
in the absence of external magnetic field.

Comparison of the Electron Configurations and Unpaired


Electrons for Various Ions
Ion Electron Number of Magnetic
Configurati Unpaired moment in Bohr
on Electrons 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+) 2d2(3p6) 2(0) 2(0)

Cr3+ (Cr2+) 2d3(3d4) 3(4) 3(4)

Mn2+ (Mn3+)(Mn4+) 2d5(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)

Ferrites are classified into three types based on their crystal


structure,
 The cubic ferrites of spinel type
 The cubic ferrites of garnet type
 The hexagonal ferrites of magnetoplumbite type
Table-1 shows the compositions and structures of these magnetic
ceramics.
Table-1: Compositions and Structures of Magnetic Ceramics
Structure Composition Application

Cubic General structure MeFe2O4, Soft magnets


where Fe is trivalent and Me is
Spinel Ferrites
divalent Ni, Mn, Mg, Zn, Cu,
Co, Cd or a mixture.

1 Fe2O3 : 1 MeO

Cubic General structure R3Fe5O12, Microwave


where Fe is trivalent and R is Y devices
Garnet Ferrites
or a trivalent rare earth, typically
Gd, Dy, Sm, Tb, Ho etc.

3R2O3 : 5 Fe2O3
Magnetoplumbites Me Fe12O19 where Me is a Hard magnets
diavalent Ba, Sr, Pb, Ca
or
1 MeO : 6 Fe2O3
Hexagonal Ferrites
BaFe12O19, SrFe12O19

PbFe12O19, CaFe12O19

Spinel Ferrites
Crystal structure of spinel ferrites
Cubic ferrites are said to have the spinel structure and are sometimes
called ferro-spinels, because their crystal structure is closely related
to that of the natural mineral spinel MgO.Al2O3=MgAl2O4(AB2O4).
The structure is complex, in that there are 8 AB2O4 molecules with
total 78 = 56 ions per unit cell. The structure was first described by
Bragg and Nishikawa in 1915. Many of the commercially important
spinels are synthetic, but one of the most important and probably the
oldest magnetic material with practical applications, magnetite
Fe3O4 is a natural oxide.
The spinel crystal structure is cubic with O2- ions forming a fcc
lattice. There are two types of interstitial sites are available in this
close-packed structure. In the unit cell containing eight formula
equivalent of MeFe2O4 there are 32O2- ions and 64 sites with
tetrahedral coordination of O2- ions around the cations called A-
sites because it is located at the centre of a tetrahedron whose
corners are occupied by four oxygen ions. There are 32 sites with
octahedral coordination of O2- ions around metal ions, called B-
sites because it is located at the centre of a octahedron whose
corners are occupied by six oxygen ions. As shown in table 2, only 8
of 64 A-sites and 16 of the 32 B-sites are occupied in a ferrite unit
cell.
Table-2: Arrangements of Metal Ions in the Unit Cell of Ferrite MeFe2O4

Kind of site Size of Number of Number of Occupants


o
site ( A ) available occupied Normal Inverse
sites sites
spinel spinel
Tetrahedral 0.5.5-
64 8 8Me2+ 8Fe3+
(A) 0.67

Octahedral 8Fe3+
3+
0.67-0.9 32 16 16Fe
(B) 8Me2+

Size of the A and B sites are also shown in Table 2 which is in the
range of 0.6-0.9 Å. Therefore the crystallographic environment of
the A and B sites are distinctly different. Fig.1 shows the schematic
representation of crystal structure of a cubic spinel ferrite unit cell.
The unit cell can be considered to contain eight octants of ions with
the configurations as shown. Octants ion the left side of the figure
with cell edge dimension of a/2 is represented by one of the shaded
blocks of the unit cell. The octant on the right is represented by one
of the unshaded blocks.
One tetrahedral A-site occurs at the centre of the right octant and
other A-sites are at various octant corners, represented by black
circles. Four octahedral B-sites are shown in the left octant. The
coordination of one B-site with six oxygen ions is indicated by six
dashed lines. Two of the oxygen ions are in adjacent octants behind
and below the ones shown. The oxygen ions are arranged
tetrahedrally with respect to the metal cations in all octants.

Normal and Inverse spinels:


Cation distribution
In the spinel MgAl2O4, Al3+ and Mg2+ cations occupy the octahedral
(B-site) and tetrahedral (A-site) sites respectively and indicated as:
(Mg2+) [2Al3+]O4
where the square brackets indicate the octahedral B-sites occupancy,
and the cations in parentheses are located in the tetrahedral A-sites.
This is the so called “normal” spinel.
The cation distribution in the spinel Me 2 Fe23O4 can be as follows.
The spinel ferrites have been classified into three categories due to
the distribution of cations on tetrahedral (A) and octahedral (B)
sites. These are
(1) Normal spinel ferrites
(2) Inverse spinel ferrites
(3) Mixed or random spinel ferrites.
(i) Normal spinel ferrites : The divalent cation (Me2+) are in
tetrahedral A-sites and two trivalent (Fe3+) cations are in octahedral
B- site which is represented as (Me2+)A[Fe3+Fe3+]BO4 . A typical
example of normal spinel ferrite is ZnFe2O4, CdFe2O4. i.e., (Zn2+)A
[2Fe3+]BO4 and (Cd2+)A [2Fe3+]BO4 normal spinel. They are
nonmagnetic i.e. paramagnetic.
(ii) Inverse spinel ferrites : In this case divalent (Me2+) cations are
in octahedral B-sites and the trivalent (Fe3+) cations are equally
divided between A and B sites (the divalent and trivalent ions
normally occupy the B sites in a random fashion i.e. they are
disordered) arrangement is as (Fe3+)A[Me2+Fe3+]BO4 where Me= Fe,
Ni, Co, Mg, and Cu. The FeO.Fe2O3=Fe3O4, NiFe2O4 CoFe2O4,
MgFe2O4, and CuFe2O4 ferrites have the inverse structure and they
are all ferromagnetic.
(iii) Mixed or random spinel ferrites: The arrangement of the
form (Me2+xFe3+1-x)A[Me2+1-xFe3+1+x]BO2-4 is often referred to as
mixed spinel, where cations in the parentheses are at (A) sites and
those in the brackets are at [B] sites and x is called the inversion
parameter.
 when x = 1; normal spinel
 when x = 0; inverse spinel
 when 0 < x < 1; mixed spinel ferrires.
Typical example of mixed spinel ferrites are (Ni-Zn)Fe2O4 , (Ni-
Cu) Fe2O4 ,(Mn-Zn) Fe2O4 . This are called mixed ferrites. They are
the solid solutions of Ni Fe2O4 and Zn Fe2O4, Ni Fe2O4 and Cu
Fe2O4, MnFe2O4 and Zn Fe2O4 respectively. Most of the cubic
ferrites used commercially are mixed ferrites.
A classical, extensively studied example of mixed ferrite is the so-
called Ni-Zn ferrites, with the general formula:
ZnxNi1-x Fe2O4
Where 0≤x≤1. Ni Fe2O4 is an inverse spinel, and Zn Fe2O4 is normal;
the cation distribution is therefore:
(ZnxFe1-x) [Ni1-xFe1+x]O4
This ferrites are the basis for many applications.

Table-3: Examples of Engineering the Magnetic Behavior of


[Spinel] Composition by Crystal Chemical Substitution.

Ferrite Postulated ion Magnetic Magnetic Magnetic Moment Magntiz Lattice


Distribution Moment Moment (B) per Molecule ation const.
(B) of (B) of MeFe2O4 emu/gm
(Å)
Tetrahedral Octahedral
Tetrahedral Octahedral Ions Ions Theor Experi at 0K
Ions (A) Ions (B)

ZnFe2O4 Zn2+ 2Fe3+  0 0 0 0 0 8.44

CdFe2O4 Cd2+ 2Fe3+  0 0 0 0 0 8.70

2+ 0.2Mn2+
0.8Mn
MnFe2O4 + 4+1 1+9 5 4.6 112 8.50
+ 0.2Fe3+
1.8Fe3+

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

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

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

Cu2+ +
CuFe2O4 Fe3+ 5 1+5 1 1.3 30 8.37*
Fe3+
2+ 0.9Mg2+
0.1Mg
MgFe2O4 + 0+4.5 0+5.5 1 1.1 31 8.36
0.9Fe3+
1.1Fe3+

Li0.5Fe2O 3+ Li+0.5 +
Fe 5 0+7.5 2.5 2.6 69 8.33
4 1.5Fe3+

*Cubic when quenched from above 7600C. If slowly cooled, it


becomes tetragonal, with a=8.77 Å and c=8.70 Å.

The normal and inverse structure is to be regarded as extreme cases,


because X-ray and neutron diffraction have shown that intermediate
structures can exist where the divalent cations are split between A
and B sites.

For example manganese ferrite, MnFe2O4 is almost, but not


perfectly, normal; instead of all the Mn2+ ions on the A-site, a
fraction of 0.8 is on A-sites and 0.2 on B-sites. Similarly magnesium
ferrite is (MgFe2O4) is not quite inverse; a fraction 0.9 of the Mg2+
ions on B-sites and 0.1 on A-sites.
In fact, distribution of the divalent ions on A and B sites in some
ferrites can be altered by heat treatment; it depends, for example, on
whether the material is quenched from a high temperature or slowly
cooled.

In case of some ferrites x depends up on the method of preparation.


If these ferrites are quenched from a high temperature, x has a value
of 1/3. For samples of MgFe2O4 and CuFe2O4 quenched from
various temperatures, the inversion has been determined by X-ray
diffraction and magnetic measurements.

It was found that the results satisfy the Boltzman distribution law,
x(1  x)  E / kT
 e
(1  x) 2
where E = 0.14eV. Neutron diffraction examination of MgFe2O4
have yielded a value of x =0.1. For MnFe2O4 distribution was found
to be (0.8Mn2+0.2Fe3+) [0.2Mn2+1.8Fe3+]O4.
The cation distributions of many spinel ferrites are shown in Table-
3.
Factors that affect cation distribution over A and B sites in spinels:
1. Size of the cations
2. Electronic configuration of cations
3. Electrostatic (Madelung) energy
4. The saturation magnetization of the ferrites.
Smaller cations (trivalent) prefer to occupy the A-sites. The cations
have special preference for A and B sites and preference depends on
the following factors:
 ionic radius
 size of the interstices
 sintering temperature
 orbital preference for specific coordination
For example: Zn2+, Cd2+, Ga3+ ,In3+, Ge4+ have strong preference for
A-sites, while Ni2+, Cr3+, Ti4+, Sn4+ have preference for B-sites.
Mg2+, Fe3+, Al3+, Mn2+, Cu2+, Co2+ are distributed among A and B
sites.

Spinel Solid Solutions:


A Large number of solid solutions can be synthesized among
various simple binary spinels. The main advantage of forming solid
solutions is that their physical and magnetic properties vary
continuously with composition, thus leading to the possibilities of
‘Material Design’ for specific application. The cations forming
spinel solid solutions are given in table 2.4 below.
Table 2.4: Cation forming spinel solid solutions.

Valence
1+ 2+ 3+ 4+
Li Mg Al Ti
Cu Ca Ti V
Ag Mn V Mn
Fe Cr Ge
Co Mn Sn
Ni Fe
Cu Ga
Zn Rh
Cd In

A classical, extensively studied example is the so called Ni-Zn


ferrites with the general formula:
ZnxNi1-xFe2O4; 0x1
In place of Zn, Cd may be substituted. NiFe2O4 is inverse, while
ZnFe2O4 and CdFe2O4 ferrite is normal. Ni-Zn ferrites are the basis
of many potential electronic applications. Similar systems are:
ZnxMn1-x Fe2O4; ZnxMg-1x Fe2O4; ZnxCo1-x Fe2O4;
Mg1-xMnx Fe2O4; ZnxCu1-x Fe2O4, and many other.
Substitution of Fe3+ have also been studied extensively; for example
Me2+ Fe3+2-x AlxO4; with Me 2+ = Fe, Co, Mg, Cu, Ni
The amount of Al3+ on tetrahedral sites, y, is plotted as a function of
x on Fig.211 to show the cation distribution. In case of Fe2+Fe3+1-x
Al3+xO4 for instance, the cation distribution is:
(Al3+xFe3+1-x)[Fe2+Fe3+]O4; 0x1
(Al3+)[Fe2+Al3+x-1Fe3+2-x]O4; 0x2
Substitution of Fe3+ by Cr3+, In3+, Ti4 has also been studied.
The spinel system containing Mn offer an additional complication:
the energy difference between Mn2+ and Mn3+ is very small, and the
following equilibrium exists:
Fe3+ +Mn2+  Fe2+ +Mn3+ ; 0.3eV
The tendency is generally to the left. Under oxidizing conditions,
however, some Mn2+ can be oxidized to produce an excess Mn3+,
creating cation vacancies. In spinels, evidence of vacancies has been
observed only in octahedral sites.

Effect of cation substitution on lattice parameter in


spinel ferrites
The lattice parameter of a spinel ferrites increases or decreases
depending on the size of the substituting cation. If the substituting
cation has larger ionic radii than the substituted cation, then the
lattice parameter will increase and vice versa. The lattice parameter
of NiFe2O4 (a = 8.34 Å) varies (increases) linearly with the
substitution of Zn Fe2O4 (a = 8.44 Å). The increase of lattice
parameter of Ni1-xZnxFe2O4 and Ni1-xCdxFe2O4 with x content is
shown in Fig-2.10. (a = 8.34 Å for NiFe2O4; a = 8.44 Å for Zn
Fe2O4; a = 8.70 Å for CdFe2O4). The experimental value of lattice
parameters for different types of ferrites are given in table-3 above.
Similar systems below can be used to calculate the lattice parameter
for different substitution.
ZnxMn1-x Fe2O4; ZnxMg-1x Fe2O4; ZnxCo1-x Fe2O4; CdxCo1-x Fe2O4
Mg1-xMnx Fe2O4; ZnxCu1-x Fe2O4, and many other
Mg1-xMnx Fe2O4; ZnxCu1-x Fe2O4, and many other
Theoretical calculation of lattice constant of spinel ferrites:
It is known that there is a correlation between the ionic radii of both
A- and B-sublattices and the lattice parameter. If the lattice
parameter is taken as a weighted average of the projections of the
octahedral and tetrahedral bond lengths on the unit cell, the lattice
parameter, a, can be approximated by the expression:
ath 
8
3 3
r
A  RO   3 rB  RO  
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:

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


where the brackets ( ) and [ ] indicate the A-site and B-site
respectively. The cation distribution is based on the following:
1. CuFe2O4 is inverse spinel structure in which half of the ferric
ions preferentially occupy the tetrahedral (A-sites) and the
other half occupies the octahedral sites (B-sites).
2. On the other hand, non-magnetic Zn ions prefer to occupy the
tetrahedral sites.

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, while CAZn and CAFé are the
concentrations of Zn2+ and Fe3+ ions on A-sites and CBCu and CBFe
are the concentrations of Cu2+ and Fe3+ ions on B-sites. Using these
formulae, the ionic radius of A-site (rA) and B-site (rB) were
calculated and given in Table.

x Chemical A-site B-site rA (Å) rB (Å) ath (Å)


formulae

0.0 CuFe2O4 Fe  3


1
Cu
2
1 
Fe13 O42 0.67 0.715 8.491

0.1 Cu0.9Zn0.1Fe2O4 Zn 2


0 .1 Fe03.9  Cu 2
0.9 
Fe13.1 O42 0.686 0.711 8.503

0.2 Cu0.8Zn0.2Fe2O4 Zn 2


0 .2 Fe03.8  Cu 2
0.8 
Fe13.2 O42 0.702 0.706 8.516

0.3 Cu0.7Zn0.3Fe2O4 Zn 2


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

0.4 Cu0.6Zn0.4Fe2O4 Zn 2


0. 4 Fe03.6  Cu 2
0.6 
Fe13.4 O42 0.734 0.697 8.541

0.5 Cu0.5Zn0.5Fe2O4 Zn 2


0. 5 Fe03.5  Cu 2
0.5 
Fe13.5 O42 0.75 0.693 8.544

0.6 Cu0.4Zn0.6Fe2O4 Zn 2


0. 6 Fe03.4  Cu 2
0.4 
Fe13.6 O42 0.766 0.688 8.566

Table below radii of Metal Ions involved in Spinel Ferrites


Metal ions Ionic Radius (Å) Metal ions Ionic Radius (Å)
Mg2+ .78 Ni2+ .78
Mn3+ .70 Cu2+ .70
Mn2+ .91 Zn2+ .82
Fe2+ .83 Cd2+ .97
Fe3+ .67 Al3+ .57
Co2+ .82 Cr3+ .64
Calculation of magnetic moment and Saturation
magnetization:
Saturation magnetization (Ms) can be measured by two ways.
Experimentally, we get saturation magnetization from Vibrating
sample magnetometer (VSM). The theoretical value of Ms for ferrite
sample depends on (a) the moment of each ion, (b) the distribution
of the ions between A and B sites, (c) the exchange interaction
between A and B sites . The net magnetization at 0 K can be
calculated as,
Ms = MB – MA
Where, MA and MB are the magnetic moment of A and B sites in
Bohr magneton. At absolute zero, where complete saturation is
attaind, the magnetization per unit mass, Ms(emu/gm) 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.
Example: Calculation of magnetic moment in Bohr magneton (nB)
and saturation magnetization, Ms (emu/gm using above equation) of
Ni0.75Zn0.25Fe2O4, Ni0.65Zn0.35Fe2O4, 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
Ni0.65Zn0.35Fe2O4 → [ Zn0.35Fe0.65]A [ Ni0.65Fe1.35]B O4
(0×0.35)+(5×0.65) (0.65×2)+(1.35×5)
= 3.25 µB = 8.05 µB
Net, nB = (8.05 µB - 3.25 µB ) = 4.8 µB
Ni0.55Zn0.45Fe2O4 → [ Zn0.45Fe0.55]A [ Ni0.55Fe1.45]B O4
(0×0.45)+(5×0.55) (0.55×2)+(1.45×5)
= 2.75 µB = 8.35 µB
Net, nB = (8.35 µB - 2.75 µB ) = 5.6 µB

Now Ms (emu/gm) can be calculated using equation for the


respective Ni-Zn ferrites are :
Molecular . weight  M s
i) When, Zn=0.25; nB 
N  B
236.73 M s
or, 4 
6.02  1023  0.927  10 20
or, Ms= 95 emu/gm
Molecular . weight  M s
ii) When, Zn=0.35; nB 
N  B
236.73 M s
or, 4.8 
6.02  1023  0.927  10 20
or, Ms= 113 emu/gm
Molecular . weight  M s
iii) When, Zn=0.45; nB 
N  B
236.73 M s
or, 5.6 
6.02  1023  0.927  10 20
or, Ms= 132 emu/gm
which corresponds well with the value of Ms (emu/gm) of 94, 115 and
130emu/gm respectively measured with SQUID magnetometer at T=5K.
It is observed that the magnetic moment increases gradually with the
substitution of non-magnetic Zn2+ ions for magnetic Ni2+ ions. Zn2+ ions
which occupied tetrahedral (A) site and replaced same amount of Fe 3+
ions to the octahedral (B) site increases the magnetization according to
the following relation: M = MB -MA. In this way the magnetic moment
should increase and attain a value of 10 µB for pure ZnFe2O4. But it
does not happen. Magnetic moment of ZnFe2O4 is zero as shown
table -3. In Figure-32.2, it is observed that the magnetic moment
increases up to Zn=0.4-0.5 and thereafter decreases gradually. This
can be explained as follows:
The reason for decrease of magnetization beyond Zn=0.5 is due to
the fact that the magnetic moment of the few remaining Fe3+ ions on
the A-sites are no longer able to align all the moment of the B ions
ant parallel to themselves, since this is opposed by the negative B-B
exchange interaction, which remains unaffacted, i.e. JAB is
comparable to JBB. When JAB<JBB, frustration of spin alignment in B
sublattice takes place and the spins are oriented at different angles
with each other. According to theory of Yafet-Kittel, the B
sublattice will then divide itself into sublattices, the magnetization
of which make an angle with each other differing from 0 or 1800.
This disturbs the parallel alignment of spin magnetic moment on B
site giving way for canted spins.The criterion for this subdivision is
that the ions within one sublattice interact less strongly with each
other than with those in the other sublattices. Zn2+ and Cd2+
substituted ferrites have the tendency of the manifestation of similar
type of canting behavior above a certain limit of their contents.

The existence of canted spin gives rise to Yafet-Kittel (Y-K) angle


which compares the strength of A-B and B-B exchange interaction.
Neel’s two sublattice model is unable to explain decrease of
magnetization. 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 𝛼YK
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) content particularly when x ≥ 0.4-0.5. The canting
angle starts to develop sizeable value when x≥0.4 due to weakening
of JAB exchange interaction. Table below shows the calculated
magnetic moment of Ni1-xCdxFe2O4 system.

Table : Calculation of Theoretical magnetic moment of Ni-Cd


ferrites

Cadmium Ni1-xCdxFe2O4 Postulated Postulated Theoretical


Content, Tetrahedral ions Octahedral ions magnetic
x & their magnetic & their magnetic moment per
moments moments molecule at 0K
in B
0.0 NiFe2O4 Fe Ni Fe 2.0
5.0 B 2.0 B 5.0B
0.1 Ni0.9Cd0.1 Fe2O4 Fe0.9 Cd0.1 Ni0.9 Fe1.1 2.8
4.5 B 0 B 1.8 B 5.5 B
0.2 Ni0.8Cd0.2 Fe2O4 Fe0.8 Cd0.2 Ni0.8 Fe1.2 3.6
4.0 B 0 B 1.6 B 6.0 B
0.3 Ni0.7Cd0.3 Fe2O4 Fe0.7 Cd0.3 Ni0.7 Fe1.3 4.4
3.5 B 0 B 1.4 B 6.5 B
0.4 Ni0.6Cd0.4 Fe2O4 Fe0.6 Cd0.4 Ni0.6 Fe1.4 5.2
3.0 B 0 B 1.2 B 7.0 B
0.5 Ni0.5Cd0.5 Fe2O4 Fe0.5 Cd0.5 Ni0.5 Fe1.5 6.0
2.5 B 0 B 1.0 B 7.5 B
0.6 Ni0.4Cd0.6 Fe2O4 Fe0.4 Cd0.6 Ni0.4 Fe1.6 6.8
2.0 B 0 B 0.8 B 8.0 B
0.7 Ni0.3Cd0.7 Fe2O4 Fe0.3 Cd0.7 Ni0.3 Fe1.7 7.6
1.5 B 0 B 0.6 B 8.5 B
0.8 Ni0.2Cd0.8 Fe2O4 Fe0.2 Cd0.8 Ni0.2 Fe1.8 8.4
1.0 B 0 B 0.4 B 9.0 B