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MME 467

Ceramics for Advanced Applications

Lecture 04
Structure of Ceramics: Part 3

Md. Rafiqul Islam


Lecturer
Department of MME, BUET, Dhaka
CRYSTAL GROUPS – THE MoS2 GROUP

Sulphur form the lattice structure with an AABB sequence

That means two S layers


right on top of each other
(AA)
Next layers sits on the
groove of second layer
(AAB)
The fourth layer follows
the third layer (AABB)

MME 467
MoS2 GROUP

B Right in between
two layers ( that are
B right on top of each
A other) there are Mo
ions at the center of
A trigonal prism.
However only half
the trigonal prisms
are occupied

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Spinel and Inverse Spinel Structures

The spinel (MgAl2O4) structure is based on FCC close-packed oxygen


sublattice, containing 32 oxygen atoms per unit cell. The metal atoms are
distributed among the fraction of 64 available tetrahedral (A+2 atoms) and
32 available octahedral (B+3 atoms) sites.

Compounds of stoichiometry AB2O4 in which A and B are divalent and


trivalent, respectively, often form as spinel.

Compounds of stoichiometry B(AB)O4 in which A and B are both divalent


often form as inverse spinel (example Fe(NiFe)O4).

Only 8 of 64 tetrahedral sites and 16 of 32 octahedral sites are occupied


Anion form an FCC sublattice,
with the unit cell contains 32
oxygen ions, 32 octahedral
holes (1/2 filled by B ions) and
64 tetrahedral holes (1/8 filled
by A ions).
Spinel (MgAl2O3) structure

The bond strength is therefore 2/4 for A2+ and 3/6 for B3+. In order to
satisfy Pauling’s second rule, each oxygen must be coordinated by
three A2+ and one B3+.

The most commercially important spinel structure ceramics by far are


soft magnetic ferrite, which is used as inductors, transformer cores,
and read/write heads for magnetic storage media.
Normal spinel ferrites: (Me2+)A[Fe3+Fe3+]BO4 :where Me =Zn,
Cd (divalent) example : ZnFe2O4 or (Zn2+)A [2Fe3+]BO4

Inverse spinel Ferrites:(Fe3+)A [Me2+Fe3+]BO4 where Me= Fe, Ni,


Co, Mg, and Cu.

Example: NiFe2O4 or (Fe3+)A[Ni2+Fe3+]BO4


SPINEL GROUP

Can you see the figure derived on the right


Take a look through the
from the left one?
marked [110] direction Can you figure out the voids?

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SPINEL GROUP
Atom on edge: contribution 1/4 How many octahedral voids
(atoms) are in this half spinel?
Atom on face: contribution 1/2
Atom inside: contribution 1

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SPINEL GROUP
TTHDRL
voids here

Find the
OCT void

Lighter color means the atom’s distance increasing


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SPINEL GROUP
This is just one unit
of Spinel and there
are seven more of
this same unit

The figure on the left represents


the whole crystal.
Q. How many FCC units are there?

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SPINEL GROUP

You can see that there are only eight tetrahedral


atoms there, lets find out where they are

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Ceramic Density Computation

n’ ( AC + AA )
r=
VC NA

r = theoretical density of ceramic


n’ = number of formula unit within the unit cell
AC = sum of atomic weights of all cations in the formula unit
AA = sum of atomic weights of all anions in the formula unit
VC = the unit cell volume
NA = Avogrado’s number = 6.023x1023 formula units/mol
On the basis of crystal structure, compute the theoretical density of
sodium chloride. Atomic radius: rNa = 0.102 nm, rCl = 0.181 nm

2 (rNa+ rCl)
n’ = 4 in FCC lattice
 AC = ANa = 22.99 g/mol
 AA = ACl = 35.45 g/mol
VC = a3 = (2 rNa+ 2 rCl )3
= 1.911 x 10-22 cm3
rNa

n’ ( AC + AA ) rCl


r= = 2.14 g/cm3
VC NA a