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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
 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 Sample 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
 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.

 But exception is available. ex

ZrO2 and CaF2
 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.
 Location of Interstitial Sites

Octahedral hole
Three in each of the
Tetrahedral hole two planes
Three anions in one
plane, and a single
anion in the adjacent
plane

 The nearest neighbour configuration of oxygen atoms around

OH and TD cations is independent of whether the basic structure
is derived from FCC or HCP.
Hexagonal structure Tetrahedral sites Octahedral site
 Interstitial Sites in Crystals

Octahedral
*
hole
Tetrahedral
hole
*

FCC structure showing tetrahedral and octahedral position

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 Interstitial Sites in FCC Crystals

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

The cation-anion distance =  radii

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 Anion-cation Coordination Configuration

stable Critically stable unstable

For 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 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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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

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
 Next Class
Lecture 3:

Crystal Structure of Ceramics: Part-2