Ceramic crystal structures

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 Metallic bonding

Chemical bonding that occurs due to electrostatic attractive force between the
conduction/free electrons (in the form of an electron cloud of delocalized electrons)
and positively charged metal ions/cations.

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 Introduction
In simple ceramic compounds, the atomic bonding is a mixture of ionic and covalent types.

The percentages of ionic and covalent character for the bonds between the atoms in these
compounds can be obtained by considering the electronegativity differences between the
different types of atoms by using Pauling’s equation.

Electronegativity: The tendency for an atom of a given chemical species to attract shared
electrons.

The amount of ionic and covalent bonding between the atoms of these compounds is
important since it determines to some extent “What type of crystal structure” will form in
the bulk ceramic compound.

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 Percent ionic character
Larger the electronegative difference between the two chemical species, more will be the
percent ionic character.

Case 1: Hypothetically, if two atoms (A and B) has the identical electronegativity, both the
species has the same tendency to attract the bonding pair electron, so it will be found on
average half way between the two atoms “A” and “B”, respectively. More or less fully
covalent character is witnessed. “A” and “B” would usually have to be the same atom in this
case.

Case 2: B is slightly more electronegative than A.

“B” end of the bond has more than its fair share of electron density and it becomes slightly
negative. On the other hand, A becomes slightly positive (Less ionic character).

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 Percent ionic character
Case 3: B is largely more electronegative than A.

“A” has lost its control of the bonding electron pair, and “B” took its complete
control over it. As a result, ions are formed and the ionic bonding between “A” and
“B” is witnessed (More ionic character).

How bonding character influences the crystal structure ?

In crystals having a large measure of ionic bond character, the structure is largely
determined on the basis of how positive ions and negative ions can be stacked
together on a lattice to maximize electrostatic attractive forces and minimize
electrostatic repulsion.

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 Packing of opposite charged ions
Anion Cation

Pauling has derived rules for achieving the minimum - energy condition based on properties
of the ions.
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 Ionic-covalent mixed bonding
• Complete transfer of charge/electron between atoms does NOT occur in
most crystalline ceramic compounds.

• Instead, the transferring electrons are shared between the neighboring

ions providing a partial covalent contribution to the chemical bond.

• The high concentration of electrons between the atoms in the crystal

results in a very strong bond.

• This type of mutually shared, partly directional bond is termed as an

ionic-covalent bond and is characteristic of most ceramic materials.

E.g. MgO.

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 Ionic-covalent bonding in MgO

Transferred electrons are shared between Mg and O in MgO ceramic compound.

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 Structural rules – radius ratio
The principles that underlie the structural characteristics of ceramic crystal
compounds can be generalized into structural rules.

(i) Achieve a maximum packing of oppositely charged ions around each reference
ion.

(ii) Preserve electrical neutrality.

Furthermore, Pauling framed the rules based on the radius-ratio of cation and anion.

The ratio of the radius of the central cation to that of the surrounding anions is called
the radius-ratio.

Pauling's Rule 1 : This radius-ratio determines the geometry for the cation to
remain in contact with each anion (at the minimum - energy distance).
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Potential energy-distance plot

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 Structural rules – Coordination number
Cations are normally smaller than the anions they are associated with.

The number of anions that surround a central cation in an ionic solid is called the co-
ordination number (CN) and it corresponds to the number of nearest neighbors surrounding a
central cation.

For stability, as many anions as possible should surround a central cation.

However, the anions must make contact with the central cation and charge neutrality must be
maintained.
Stable, but distorted Stable Unstable

Stable and unstable

configurations of
ionic solids:

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 Stable and unstable configurations
If the anions do not touch the central cation, the structure becomes unstable because the
central cation can "rattle" around in its cage of anions.

The radius-ratio, when the anions just touch each other and contact the central cation is called
the critical (minimum) radius ratio.

Allowable radius-ratios for ionic solids with co-ordination numbers of 2, 3, 4, 6, 8, 12 are

listed in the following table.

Only position
of anions is
shown.

12
Only position
of anions is
shown.

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 Stable and unstable configurations

The critical radius-ratios derived are useful, but not always exact
because in some cases the electronic configuration of an ion is
distorted or polarized, by the presence of neighboring ions.

That is, no longer spherical symmetry is maintained due to

distortion.

This is particularly true for high atomic weight, large, easily

distorted anions adjacent to small highly charged cations.

Similarly, contributions of directional covalent bonding have an

effect.

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 Polyhedra configuration
Tetrahedron configuration Octahedron configuration

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 Sharing of polyhedras
Pauling's Rule 2 :
The existence of faces or edges common to two polyhedra influences the
structure's stability.

Many oxide and silicate structures can be built up by combining regular

tetrahedral or octahedral polyhedras.

They can be linked together by having a corner in common or sharing an edge or a

face.

The shared corner arrangement is much more stable than the shared edge, and
shared faces practically never occur.

The order of stability decreases because the two positively charged central cations
are brought progressively closer in the ratio 1 : 0.58 : 0.33 for a shared corner :
edge : face, and the electrostatic repulsion energy is greatly increased.

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 Sharing of polyhedras

Sharing of polyhedra influences the crystal structure stability.

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 Cation valency and bond strength
Pauling's Rule 3 :
Third rule is based on the necessity for neutralizing the +ve and -ve charge associated with
each anion and cation.

The 3rd rule states that in a stable structure, the total strength of the valency bonds which
reach an anion from all neighboring cations is equal to the charge of the anion
Si2O7 structure
Bonds = line joining each cation with anions surrounding it.

For Silicon with tetrahedral coordination of 4 : Bond Strength = 4/4 =1

For Al3+ with octahedral coordination of 6 : Bond Strength = 3/6 = ½

For Si2O7 structure : Two bonds with a strength of 1 each reach the central oxygen ion for a
total bond strength of 2, which is the oxygen ion valency.

The large majority of structures necessary for understanding ceramic materials can be
understood either on the basis of closed-packed structure or on the basis of rules for forming
co-ordination compounds.

Bond strength – Ratio of cation valency to number of bonds. 18

Fact: Tetrahedral and octahedral voids

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