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Octahedral And Tetrahedral Voids In FCC

BY HASNA RIAZ
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
Voids
atom. Types of
• These voids have complicated shapes; but we are mostly interested in the largest sphere voids in FCC
Tetrahedral
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
other.

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
atoms.
• 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
translations.

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

C.N=6
4 face centered Are present in the
atoms plane of the paper

Number of
octahedral Zeffective = 4
Octahedral voids= Zeffective
Voids

Rc/Ra = 0.414 1 Body


Position at ½ , ½ , ½
centered

Present at 2 12/4 =3
position
Edge Position at ½ , 0, 0
Centered
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
cell
C.N = 4
3 at face centred
position of unit cell

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


voids = 2*Zeffective 8
Tetrahedral
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
References:
1. Introduction to ceramics by Kingery Bown Uhlmann
2. The Science and Engineering of Materials by Donald R.Askland
3. www.slideshare.net