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Lecture 02
Crystal Structure of Ceramics: Part-1
Ref: (1) Introduction To Ceramics- Kingery
(2) Ceramic Materials- Science and Engineering- Carter & Norton
Octahedral hole
Three in each of the
Tetrahedral hole two planes
Three anions in one
plane, and a single
anion in the adjacent
plane
Octahedral
*
hole
Tetrahedral
hole
*
There are 4 octahedral voids per fcc cell There are 8 tetrahedral voids per fcc cell
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Interstitial Sites in FCC Crystals
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Interstitial Sites in HCP Crystals
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Interstitial Sites in BCC Crystals
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Pauling’s Rules
Structure is determined on the basis of how negative and positive
ions can be packed.
- +
Electrostatic attractive forces
Electrostatic repulsion
- -
Certain generalization have been made which
interpret maximum crystal structure known
as Pauling’s Rule + +
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A coordinated polyhedron of anions is formed about
each cation, the cation-anion distance being
determined by the radius sum, and the coordination
number of the cation by the radius ratio
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Anion-cation Coordination Configuration
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Coordination # and Ionic Radii
r
cation
• Coordination # increases with
r anion
rFe+2 0.077 nm
= 0.550
rO-2 = 0.140 nm
The value lies between 0.414 and 0.732. Thus the CN is 6.
Since both Fe and O has the same valence, both Fe and O have the same CN of 6.
Therefore, the predicted crystal structure of FeO will be ROCKSALT.
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Justification for NaCl, CsCl and Al2O3 etc.
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The existence of edges, and particularly of faces,
common to two anion polyhedra in a coordinated
structure decreases its stability;
This effect is large for cations with high valency and
small coordination number,
It is especially large when the radius ratio approaches
the lower limit of stability of the polyhedron
examples
– Don’t let like charges get near each other
– Share edges or corners, not faces
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Rule 4: Sharing Polyhedral
Cations with high valency and low coordination numbers tend to not
share their coordinating polyhedra.
Pauling’s fourth rule says that highly charged cations will tend to be
as far apart as possible to minimize electrostatic repulsion.
Ti 4+ shares corner
Perovskite
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Rule 5: Parsimony
tends to be small.
If all types of bonding are possible, it is difficult to predict what will
happen
Next Class
Lecture 3: