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Octahedral And Tetrahedral Voids In FCC

FCC Unit Cell:
• If we start with a layer of atoms closely placed and then add a second layer we can go on to
add a third layer in two ways.
• If the third layer is not directly above previous layers, we end up with a face-centered cubic
lattice. However, if the third layer is directly above the first the packing is equally dense but
has a different structure, called hexagonal close packing.

Discovery: It was in 1912 that Max von Laue and co-

workers discovered that when X-rays were shone through a
crystal of copper sulphate, the crystal acted like a grating
and produced a diffraction pattern that could be measured
on photographic film.
Brag’s used Max Von Laue work to determine the very first
crystal structures from their diffraction patterns
Voids In FCC:
• Packing fraction is always smaller than 1 which implies that there are void between the Octahedral
atom. Types of
• These voids have complicated shapes; but we are mostly interested in the largest sphere voids in FCC
which can fit into these voids. Voids
• Once we know the position of a void then we can use the symmetry operations of the
crystal to locate the other voids. This include lattice translations.
• When an atom is added to a pure crystal, the atom added may ‘sit’ in a space between
the atoms, in this way void greater than some critical values are filled.

For a stable co-ordination, anion and

cation must be in contact with each

If Rc/Ra > Ideal , then cation remains in

contact with anion. But cation forces
the anion apart.
Octahedral Voids:
• Octahedral void is formed by 6 face centered atoms in FCC unit cell.
• At edge, octahedral void is produced by 2 corner atoms and 4 face centred
• At the centre of every edge there is one octahedral void present, and 1 is at
the centre of the cube.
• So, the Zeffective for number of octahedral voids per unit cell will be:
Number of O.V= [12*(1/4)] + 1 =4

Produced by arrangement of layers

opposite to one another. And make
shape like octahedron
Once we know the position of a void then we
can use the symmetry operations of the crystal to
locate the other voids. This includes lattice

Location of the Octahedral void:

At body centre {½, ½, ½}
At edge centre {½, 0, 0}
Voids/cell=4 2 corner Present above and below
atoms in symmetrical position

4 face centered Are present in the
atoms plane of the paper

Number of
octahedral Zeffective = 4
Octahedral voids= Zeffective

Rc/Ra = 0.414 1 Body

Position at ½ , ½ , ½

Present at 2 12/4 =3
Edge Position at ½ , 0, 0
Tetrahedral Voids:
• Voids surrounded by 4 sphere in a lattice is called Tetrahedral void.
• It is formed by 3 face centered atoms and 1 corner atom in a unit cell.
• The depression of the 3 atoms in 1st layer covered by 1 atom from the 2nd layer produce a void
called as tetrahedral void
• They are present at ¼ distance from the corner of a body diagonals. One body diagonals have
2 tetrahedral voids.
• So the Zeffective for number of tetrahedral voids per unit cell is
No of T.V = 4*2 = 8
Voids/cell=8 1 at corner of unit
C.N = 4
3 at face centred
position of unit cell

No of tetrahedral No of T.V= 4*2 =

voids = 2*Zeffective 8
voids in FCC
Rc/Ra= 0.225

2 T.V at each body

Present at body diagonal of unit
diagonals cell

¼ way along body

Position Of T.V
diagonal {¼, ¼, ¼},
along body diagonal
{¾, ¾, ¾}
Occupation Of Octahedral Voids in FCC:

Figure 1 shows the crystal structure of MO types in which octahedral

voids are filled

In this crystal structure the co-ordination number of M and O is 6:6.

All octahedral are occupied with cations.
Example: MgO, BaO
Figure 1

Occupation of Tetrahedral Voids in FCC:

Figure 2 shows the crystal structure of MO type in which tetrahedral
voids are filled

In this crystal structure the co-ordination number of M and O is 4:4

½ of tetrahedral voids are occupied.
Example: BeO
Figure 2
Anti- Fluorite type crystal structure Fluorite type crystal structure
M2O type crystal structure MO2 type crystal structure
1. Introduction to ceramics by Kingery Bown Uhlmann
2. The Science and Engineering of Materials by Donald R.Askland