Crystal Structure of

Ceramics
Lecture 4

Ceramics and Composites Technology

MM451 Course (3 Credits)
B.Tech- MME
4th year- 2nd Sem
2022-2023
Dr. G. Ramya Sree
Metallurgical and Materials Engineering
NIT Warangal
Ceramic Materials

• Crystal structure: the arrangement of ions and

atoms in crystalline ceramics
• Crystalline compounds of metal (Al, Si, Mg, Zr, Ti,
Ca, Be,….) and non-metals ( O,N,C,B)

• Bonded with ionic bond and/or covalent bonds.

• Simple compounds (MgO, Al2O3, SiC, Si3N4)
• And also complex phases (silicates)
• Properties → differences in bonding
• The densities are small (2000-4000 kgm-3)
• Heavy metals → UO2 and ThO2

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Ceramics

3
Ceramics

• Covalently bonded compounds→

• 3D network→ diamond, SiC, Si3N4
• Layered structure→ graphite, mica, talc or clays
• Fibrous chains structure→ asbestos

• High hardness
• Superior chemical inertness
• Brittleness
• Low thermal expansion
• Low electrical conductivity

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Ceramics

• Ionically bonded compounds→ NaCl, CaF2, MgO

• Group I, II → Group VI, VII
• Large difference in electronegativity
• Hence are strong tendency →for ionic bond

• Low ductility
• High thermal expansion
• Low electrical conductivity

• Ionic conduction at high-temperature→ ZrO2

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Ceramics crystals
Ceramics, by definition, are composed of at least two elements, and consequently
their structures are, in general, more complicated than those of metals.

Three categories

1. AX type
2. AmXn type
3. AmBnXp type

A → metal atom
X → non-metal atom
m n
B → non-metal atom
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Ceramics crystal → AX type
The unit cell of CsCl

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The unit cell of ZnO
Ceramics crystal → AX type

The unit cell of NaCl

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Ceramics crystal → AX type

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Ceramics crystal → AX type

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Ceramics crystal → AmXn type

Ca
F2

Two unit cells of Calcium Fluorite (CaF2)

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Ceramics crystal → AmXn type

Rutile has a tetragonal unit cell, with unit

cell parameters a = b = 4.584 Å, and c =
2.953 Å. The titanium cations have a
coordination number of 6, meaning they
are surrounded by an octahedron of 6
oxygen atoms. The oxygen anions have a
coordination number of 3, resulting in
trigonal planar coordination.

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Ceramics crystal → AmXn type

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Ceramics crystal → AmXn type

Al2O3
Crystal
Structure

The C layer is
only two-thirds
full

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Ceramics crystal → AmBnXp type

Perovskite → CaTiO3

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Ceramics crystal → AmBnXp type

Spinels → MgAl2O4 (MgO.Al2O3)

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Ceramics crystal → Factors affecting
1. Crystal Stoichiometry
• Any crystal has to be electrically neutral.
• This requirement places severe limitations on
the type of structure the ions can assume.
2. Radius ratio
• To achieve the state of lowest energy, the
cations and anions will tend to maximize
attractions and minimize repulsions.

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Ceramics crystal → Factors affecting

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Ceramics crystal → Factors affecting

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Ceramics crystal → Factors affecting
3. Propensity for covalency and tetrahedral
coordination:
In many compounds, tetrahedral coordination is observed despite the fact
that the radius ratio would predict otherwise. For example, many
compounds with radius ratios greater than 0.414 still crystallize with
tetrahedral arrangements such as zinc blende and wurtzite. This situation
typically arises when the covalent character of the bond is enhanced, such
as when

• Cations with high polarizing power (for example, Cu2+, A13+, Zn2+,
Hg2+)are bonded to anions that are readily polarizable26 (I- , S2 - , Se2-). As
discussed in greater detail in Chap. 4, this combination tends to increase
the covalent character of the bond and favor tetrahedral coordination.

• Atoms that favor sp3 hybridization, such as Si, C, and Ge, tend to stabilize
the tetrahedral coordination for obvious reasons.

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Thank You

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