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

That
Sulphur form the lattice structure with an sequence
AABB 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)
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 MoS2 GROUP

B Right in between
two layers ( that
B are right on top of
A each other) there
are Mo ions at the
A center of 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.
 Types of spinel Ferrite
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

Take a look
derived on the right from
through the the left one?
marked [110] Can you figure out the
direction
MME 467 voids?
 SPINEL GROUP How many
Atom on edge: octahedral voids
contribution 1/4 (atoms) are in this
Atom on face:
contribution 1/2
Atom inside: half spinel?
contribution 1

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 SPINEL GROUP
TTHDR
L 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
The figure onunit
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 =
V C NA

r = theoretical density of ceramic

n’ = number of formula unit within the unit cell
SAC = sum of atomic weights of all cations in the formula unit
SAA = 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
S AC = ANa = 22.99
g/mol
S AA = ACl = 35.45
g/mol
VC = a3 = (2 rNa+ 2 rCl )3 rNa
= 1.911 x 10-22 cm3

n’ ( AC + AA ) rCl

r= = 2.14 g/cm3
VC NA a