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Al3+ 2p6 0 0
O2- 2p6 0 0
Sc3+ 3p6 0 0
Fe2+ 3d6 4 4
Fe3+ 3d5 5 5
1 Fe2O3 : 1 MeO
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 78 = 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
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.
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+
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.
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