Chapter 11 (from Smith)

or

CHAPTER 12 (From Callister)

STRUCTURE AND PROPERTIES OF

CERAMICS

Chapter 12-

CHAPTER 12: STRUCTURE AND

PROPERTIES OF CERAMICS
ISSUES TO ADDRESS...

Structures of ceramic
materials:
How do they differ from
that of metals?

Chapter 12- 1

Ceramic
Ceramic materials are inorganic, nonmetallic materials that consists
of metallic and nonmetallic elements bonded together primarily by
ionic or covalent or mixed (ionic and covalent) bonds.
Ceramic materials are hard and brittle with low toughness and
ductility.
They are good electrical and thermal insulators.
The word ceramic comes from the Greek word
"keramikos", which means "pottery
Two types of ceramics
Traditional ceramics: (made up of clay, silica)
Ex. Glass, bricks and tiles

Engineering ceramics: (Pure compounds)

Ex. Al2O3, SiC

Chapter 12-

 The atoms in ceramic materials are held

together by a chemical bond

Briefly though, the two most common chemical

bonds for ceramic materials are covalent and
ionic.

Covalent and ionic bonds are much stronger

than in metallic bonds and, generally speaking,
this is why ceramics are brittle and metals are
ductile.
The main compositional classes of engineering
ceramics are the oxides, nitrides and carbides.

Chapter 12-

 Ceramics have ionic or covalent bonding

Crystal structure is strongly influenced
by bonding
This influences mechanical and physical
properties. e.g.
! little ductility at room temperature

Chapter 12-

CERAMIC BONDING
Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.

Large vs small ionic bond character:

Chapter 12-

Different types of ceramic structures

Oxide structures:cubic closed packed structure
Rock Salt (NaCl), Wurtzite (BeO),
Zinc Blende (ZnS),Spinel (MgAl2O4),
Corundum (Al2O3),Rutile (TiO2,GeO2 ,PbO2,SnO2),
Cesium Chloride, Fluorite (CaF2),
Perovskite (BaTiO3),Ilmenite (MgTiO3)
Silicate structures:
Silica (SiO2), Orthosilicates(Fe2SiO4),Pyrosilicates(Si2O7)

Chapter 12-

Conditions for a stable configuration

Anions and cations should always touch
each other
Anions generally will not touch each
other,but they should be in close contact
Maximum possible number of anions
should surround the central cation for
max. reduction in the electrostatic
energy,
rc<ra
[0< rc/ra<1] ,
depending on this range we get different
cation-anion configurations
Chapter 12-

STABLE AND UNSTABLE CONFIGURATIONS

Coordination number is the no. of anions surrounding

the central cation

Chapter 12-

Chapter 12-

Chapter 12-

AX- Type crystal structure

Rock Salt Structure or NaCl Structure
Highly Ionically bonded with Na+ ions occupying interstitial sites
between FCC and Cl- ions.
Radius ratio = 0.56, CN = 6.
MgO, CaO, NiO and FeO
have similar structures.

Chapter 12-

Cesium Chloride Crystal Structure

CsCl is ionically bonded with radius ratio = 0.94 and CN = 8.

Eight chloride ion surround a central cesium cation at the ( , ,
) position.

Chapter 12-

Zinc Blende (ZnS) Crystal Structue

Four zinc and four sulfur atoms.

One type (Zn or S) occupies lattice points and another
occupies interstitial sites of FCC unit cell.
S Atoms
(0,0,0) ( , ,0) ( , 0, ) (0, , )
Zn Atoms
( , , ) ( , , )( ,, ) ( , , )
Tetrahedrally covalently bonded
(87% covalent character) with
CN = 4.

Chapter 12-

AmXp- Type crystal structure

If the charges on cations and anions are not same, a compound
can exist with the chemical formula AmXp
Fluorite (CaF2) is a example of
AmXp- type crystal structure.
Radius ratio rC/rA = 0.8
CN (cation- anion) = 8
CN (anion- cation) = 4

Chapter 12-

Flurite (CaF2)

Chapter 12-

AmBnXp- Type crystal structure

Ceramic compound may have more that one type of cation. For
two types of cations (Represented by A and B), the chemical
formula may be designated as AmBnXp
Perovskite (CaTiO3) crystal structure
BaTiO3 (Barium titanate) has a perovskite crystal structure
above 120oC. Below this temperature the structure is slightly
changed.

Chapter 12-

BaTiO3 (Barium titanate) crystal structure.

CN (cation A- anion) = 12
CN (cation B- anion) = 6
CN (anion- cation) = 6

Chapter 12-

Crystal structure from the closed

packing of anions
In ceramics, the closed packed planes are composed anions.
Small interstitial sites are created (in which cations may reside)
when there planes are stacked
In the FCC or HCP crystal structures, which are closed- packed
structures, there are two types of interstitial sites
Octahedral and Tetrahedral

Chapter 12-

Octahedral and Tetrahedral voids

CN for cation filling tetrahedral position is 4

CN for cation filling octahedral position is 6

Chapter 12-

Chapter 12-

Chapter 12-

CERAMIC DENSIY COMPUTATION

Theoretical density , of a crystalline ceramic
material,

n'

AC
AA
VC N A

n=the number of formula units (all the ions that are

included in the chemical formula unit) within the
unit cell, in BaTiO3, there is one Barium ion, a
titanium ion and three oxygen ions
Ac=the sum of the atomic weights of all cations in
the formula unit
AA=the sum of the atomic weights of all anions in
the formula unit
V c=unit cell volume
NA= Avogadros number
Chapter 12-

Solution

Chapter 12-

Ex.1
Predict the coordination number of the cations and the crystal structure
of the ceramics consisting of ions of radii as given in three sets:
Ceramic I :
Ni2+ = 0.069 nm, O2- = 0.140 nm
Ceramic II :
Ca2+ = 0.100 nm,
F- = 0.133 nm
Ceramic III : Mg2+ = 0.072 nm, O2- = 0.140 nm

1.Ceramic I.: C. N. of Ni2+ - 6

Crystal Structure Rock salt (NaCl type)

2. Ceramic II : C. N. of Ca2+ - 8
Crystal Structure Fluorite

3.Ceramic III : C. N. of Mg2+ - 6

Crystal Structure Rock salt (NaCl type)

Chapter 12-

Structure

Rock salt
structure

No. of molecules
per unit cell

No. of formula units

with in unit cell

Coordination
Number

Chapter 12-

Structure

Cesium
Chloride

No. of molecules
per unit cell

No. of formula units

with in unit cell

Coordination
Number

Chapter 12-

Structure

Zinc Blende

No. of molecules
per unit cell

No. of formula units

with in unit cell

Coordination
Number

Chapter 12-

Structure

Fluorite

No. of molecules
per unit cell

No. of formula units

with in unit cell

Coordination
Number

4
CN (cation- anion) = 8
CN (anion- cation) = 4

Chapter 12-

Structure

Perovskite

No. of molecules
per unit cell

No. of formula units

with in unit cell

Coordination
Number

CN (cation A- anion) = 12
CN (cation B- anion) = 6
CN (anion- cation) = 6

Chapter 12-