MME 467

Ceramics for Advanced Applications

Lecture 02
Crystal Structure of Ceramics: Part-1
Ref: (1) Introduction To Ceramics- Kingery
(2) Ceramic Materials- Science and Engineering- Carter & Norton

Md. Rafiqul Islam

Lecturer
Department of MME, BUET, Dhaka
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 Common Ceramic Crystal Structures

Structure Structure Atomic CN CN Example

Type Name Packing Cation Anion of Structure

AX Rock salt FCC 6 6 NaCl, MgO, FeO

AX Cesium chloride Simple Cubic 8 8 CsCl
AX Zinc blende FCC 4 4 ZnS, SiC

AmXp Fluorite (AX2) Simple cubic 8 4 CaF2, UO2, ThO2

AmXp Corundum HCP Al2O3, Fe2O3

AmBnXp Perovskite (ABX3) FCC 12(A), 6(B) 6 BaTiO3, SrZrO3

AmBnXp Spinel (AB2X4) FCC 4(A), 6(B) 4 MgAl2O4, FeAl2O4

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 Crystalline Ceramic Structures
 Most ceramic structures based on
1. either FCC, SC or HCP close-packing of one type of ion,
2. with the other ions occupying a specific set of interstitial
 sites.
Generally the larger
ions (usually
anions) form the
close packed
structure, with
smaller ions
(cations) occupying
the interstices.

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 Two principle types of cation sites, tetrahedral (TD) and
octahedral (OH), exist between layers of close-packed atoms.
 the caions need to fit snugly, so they squeeze into holes that are not quite big enough
 funny things happen if the hole size is bigger than the size of inclusion atom !!
(as in barium titanate)

 Having determined what types of holes are available, we must

now decide:
(a) Which sites are occupied by a given cation  This is determined by the radius ratio.
(b) How many sites are occupied  This is determined by the stoichiometry.

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 Hexagonal structure Tetrahedral sites Octahedral site
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 Interstitial Sites in Crystals

Octahedral
hole
*
Tetrahedral
hole
*

FCC structure showing tetrahedral and octahedral position

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 Interstitial Sites in FCC Crystals

here are 4 octahedral voids per fccThere

cell are 8 tetrahedral voids per fcc cell

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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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 Rule 1:
Interatomic distances and coordination

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

The cation-anion distance = 

radii

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 Anion-cation Coordination Configuration

stable Critically stable unstable

a specific CN, there is a critical or minimum radius ratio

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 Coordination # and Ionic Radii
r
cation
• Coordination # increases with
r
anion
To form a stable structure, how many anions can
surround around a cation?
rcation Coord ZnS
ranion No (zinc blende)
< 0.155 2 linear

0.155 - 0.225 3 triangular NaCl

(sodium
0.225 - 0.414 4 tetrahedral chloride)

0.414 - 0.732 6 octahedral CsCl

(cesium
chloride)
0.732 - 1.0 8 cubic
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 Predicting Structure Based on rC/rA Ratio

Example Problem 13.2/Callister/P-391 Ionic radius:

On the basis of ionic radii, which crystal structure Fe2+ = 0.077
would you predict for FeO? Fe3+ = 0.069
O2- = 0.140

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.

Conclusion: It is not only the chemical formula which

determine the crystal structure but also the relative sizes of the
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cations and anions.
 Rule 2: Electrostatic valency principle
In a stable ionic structure, the valence of each
anion, is exactly or nearly equal to the sum of
the strengths of the electrostatic bonds to it
from the adjacent cations
The strength of an ion’s bond may be
expressed as the ratio of its charge (z) to its
coordination (CN): Bond strength = z / CN
In other words, ions with high charges that are
bonded to few neighboring ions have the high
bond strengths.

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Justification for NaCl, CsCl and Al2O3 etc.

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 Rule 3: Sharing
polyhedral
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

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 – 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

The number of essentially different kinds of constituents in a

crystal tends to be small.

The environment of chemically similar atoms will be similar.

If all types of bonding are possible, it is difficult to predict what

will happen

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 Next Class
Lecture 3:

Crystal Structure of Ceramics: Part-2

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