Structure and Properties of Ceramics

Ceramic Materials

The Figures used in these slides are taken from:

Materials Science and Engineering: An Introduction

by

William D. Callister, Jr.

David G. Rethwisch

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

CERAMIC MATERIALS

They are non-metallic materials and inorganic
compound consisting of metallic and
nonmetallic elements.

Examples: Clay, glasses, silica (SiO2), alumina

(Al2O3), silicon carbide (SiC), silicon nitride (Si3N4),
Magnesia (MgO), zirconia (ZrO2) etc

CERAMIC STRUCTURES

Ceramics have complex crystal structures since

they contain at least two elements.

Atomic bonding ranges from total ionic to total
covalent.

Ceramics having predominantly ionic bonding
contains positively charged cations and negatively
charged anions.

The ceramic compound must be electrically
neutral. The composition must achieve a balance
between cations and anions.

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

In most cases rc/ra < 1 where rc and ra are radii of

cations and anions respectively, i.e. cations are
generally smaller than the anions.

Each cation prefers to have as many nearest anion

neighbors as possible and vice versa.

A stable ceramic structure is formed when anions

surrounding a cation are all in contact with that the
cation.

For a specific coordination number, there is a

minimum rc/ra for which cations and anions are in
contact.

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Different classes of ceramic

crystal structures.

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

AX - TYPE CRYSTAL STRUCTURES

In ceramic materials having AX crystal structure, the

number of anions equals the number of cations.

In AX compound A denotes cation and X the anion

There are several different crystal structures for AX

compound.

Examples AX-type crystal structures include:

a. Rock salt structure
b. Cesium Chloride structure
c. Zinc blende structure

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Rock Salt or NaCl Structure

The unit cell for this structure is generated from

an FCC arrangement of anions in which one
cation is located at the cube center and at the
center of the 12 cube edges

The structure can also be viewed as FCC
arrangement of the cations with anion situated at
the cube center and center of the edges

The coordination number for both cations and
anions is 6
How many numbers of Cl ions in this unit cell ?

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Cesium Chloride Structure (CsCl)

The unit cell of CsCl structure is a cube in which a

cation is located at the cube center while 8
anions are situated at each of the cube corners.

Interchange of cations and anions produce the same
structure

The Coordination number is 8 for both cations and
anions

Note that this structure is not BCC because different
atoms are involved

How many numbers of Cl- ions in this unit cell ?

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Zinc Blende Structure (ZnS)

The unit cell of zinc blende structure is a cube in
which each corner and face position is occupied by
anions while the cations fill the interior tetrahedron
positions.

The coordination number is 4

An equivalent structure can be obtained if the
position of anion and cations are reversed.

Example of crystals having this structure include
ZnS, ZnTe, SiC

How many numbers of S2- ions in this unit cell ?

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

AmXp – TYPE CRYSTAL STRUCTURES

The charges on anion and cations are different.

To maintain electrical neutrality the number of
cations and anions forming AmXp compounds are
not equal.

An example of AmXp compounds is CaF2 for which
the unit cell is a cube

One cubic unit cell of CaF2 consists of 8 cubes. F-
ions are located at the corners of each of these
cubes, while Ca2+ ions are located at the centers
of four of the cubes

The CN for cation is 8 while the anion has CN of 4.
How many numbers of F- ions in this unit cell ?

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

AmBnXp – Type Crystal Structure

A common example of AmBnXp compounds is BaTiO3

There are two cations (Ba2+ and Ti4+ ions) and one
anion (O2- ion)

A unit cell is a cube: Ba2+ ions are located at all eight

corners of the cube, a Ti4+ ion are located at the cube
center while O2- ions are located at the center of the
faces of the cubes

BaTiO3 has a perovskite structure and have very

interesting application in the electronic industry –
piezoelectric.
How many numbers of Ti4+ ions in this unit cell ?

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

CARBON

Carbon is a unique material, which does not
essentially fall within any of the major categories of
engineering materials, i.e. metals, polymers or
ceramics.

It exits in many different polymorphic forms:

Carbon

Diamond Carbon
nanotubes
Graphite

Fullerenes

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics
Diamond

Metastable polymorphic form of carbon at room
temperature

Crystal structure similar to that of zinc blende
structure in which carbon occupies all positions

Properties of diamond include
a. Extreme high hardness
b. Low electrical conductivity
c. High thermal conductivity
d. Optical transparency in visible and infra-red regions
of electromagnetic spectrum

Industrial use: cutting and grinding tools

How many numbers of C atoms in this unit cell ?

Diamond
cubic unit
cell

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Graphite

Graphite is a more stable polymorphic form of carbon
than diamond at ambient temperature and pressure

The structure of graphite consists of layers of
hexagonally arranged carbon atoms

Each atom within the layer is bonded to three other
atoms by strong covalent bonds, while adjacent layers
are bonded together by weak van der Waals bonds

The weak secondary bonds between the layers make
it possible for the adjacent layers to slide over one
another resulting in good lubrication properties of
graphite.

The properties of graphite are strongly anisotropic

Hexagonal
structure of
graphite

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Properties of graphite among others include:

a. high strength
b. good chemical stability at high
temperatures in non-oxidizing environment
c. high thermal conductivity
d. relatively high electrical conductivity in
directions parallel to the hexagonal layers
e. low coefficient of thermal expansion
f. high thermal shock resistance
g. good machinability

Industrial application: heating elements for electric

furnaces, electrodes for arc welding, melting
crucibles, high temperature refractories, insulation…

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Fullerenes

Structure of C60 (Football) und C70 (Rugby-Ball) fullerene

Fullerenes were discovered very recently – 1985

They are the first discrete molecular form of
carbon to be discovered and consist of hollow
spherical cluster of carbon atoms containing, for
example 60, 70 or 80 atoms

While fullerenes are molecular form of carbon,
graphite and diamond are solids containing
network of carbon atoms

Most common fullerines are those containing 70
and 80 atoms and are designated as C70 and C80
fullerenes respectively

Potential applications; electronics industry,
molecular sieves, gas storage, sensors, solar
cells, manufacture of diamond and diamond
coatings.
Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Carbon Nanotubes

Carbon nanotube is another molecular form of

carbon

It consists of sheets of graphite rolled into
concentric tubes with both ends capped with C60
fullerene hemispheres

Carbon nanotubes are extremely strong and stiff

They have low densities

Depending on the orientation of the tube wall,
nanotube behave electrically like a metal or a semi
conductor

Potential applications: field emitters, diodes and
transistor, hydrogen storage etc

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

IMPERFECTION IN CERAMICS

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

IMPERFECTION IN CERAMICS

Points defects

Examples are anion vacancy, cation vacancy

and cation interstitial.

Anion interstitials are improbable, why ?

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Because of the need to maintain electro-neutrality,

defects do not occur alone

For instance a cation vacancy may be accompanied
by a cation interstitial to maintain electro-neutrality.
Such a defect containing a pair of cation vacancy and
cation interstitial is called Frenkel defect

Also a cation vacancy can be accompanied by an
anion vacancy in order to maintain electroneutrality.
The defect containing a pair of cation vacancy -anion
vacancy is called Schottky defect

There can also be interstitial or substitutional

impurities in ceramic compounds as in the case of
metals.
Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Mechanical Properties of Ceramics

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Mechanical properties of Ceramic Materials

Ceramic materials are very brittle at room

temperatures and will fracture before any plastic
deformation can occur.

For Brittle Materials, fracture strength is far less than
the predicted values based on atomic bonding
energy.

Reasons:
⇒ Presence of many flaws and cracks in brittle
materials

⇒ These flaws can cause concentration or

amplification of stress at the crack tip

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch
 Structure and Properties of Ceramics

Flexural Properties of Ceramics

Mechanical properties of ceramic are usually
determined using bending rather than tensile test due
to the following reasons:
a. Tensile specimens are difficult to fabricate from ceramic
materials
b. It is difficult to grip ceramic materials without fracturing
them
c. Ceramic materials fail at about less than 0.1 % strain,
which make it compulsory for tensile specimens to be
perfectly aligned to avoid bending stresses

Effect of Porosity on Properties of Ceramics

Many ceramic materials contain pores and voids
that form during the fabrication process.

Both the flexural strength and modulus of
elasticity of ceramic materials decrease with
increasing volume fraction of porosity

Two reasons for deleterious effects of porosity on
strength are:
a. Pores reduce the effective cross-section area
across which the load is applied
b. Pores acts as stress raisers

Ref.: Mater. Sci. & Eng. An Intro. by William D Callister Jr. & David G. Rethwisch