NON-METALLIC

MATERIALS
MATERIALS SCIENCE

NON-METALLIC MATERIALS
1. CERAMICS
2. REFRACTORIES
3. GLASSES
4. POLYMERS

CERAMICS
DEFINITION

Ceramic materials are complex

compounds and solutions containing
both metallic and non-metallic
elements, which are having ionic or
covalent bonds.
Examples:
Bricks,
Glass, Tableware, etc.

Refractories,

CERAMICS

Bonding and structure

Properties of ceramic materials

Ceramic processing

BONDING AND STRUCTURE

Completely ionic,
Completely covalent and

Combination of both ionic and

covalent bonding.

BONDING AND STRUCTURE

For ionic crystals the crystal

structure is influenced by two
factors:

i.

The magnitude of the electrical

charge on each of the component
ion (because the crystal to be
neutral all the +ive charge should
balance the no. of ive charge)

BONDING AND STRUCTURE

ii. The ionic radius ratio (rc/ra) of cation(rc)and anion(ra) (because each
cation prefer to have as many
nearest
neighbor
anion
as
possible)

BONDING AND STRUCTURE

Coordination
Critical
No.
(rc/ra) value
2

(rc/ra) stability
range

Geometry

0<rc/ra < 0.155

( leanier)

0.155

0.155 rc/ra < 0.225

( triangular)

0.225

0.225 rc/ra < 0.414

(tetrahedral)

BONDING AND STRUCTURE

6

0.414

0.414 rc/ra < 0.732

( octahedral)

12

0.732

1.0

0.732 rc/ra < 1

rc/ra = 1

( cubic)
FCC or HCP

BONDING AND STRUCTURE

Examples
for
ionic
bonded
structures: Sodium chloride, Cesium
Chloride, Perovskite, etc
For covalent crystals the crystal
structure is influenced by the
directionality of bonding.

BONDING AND STRUCTURE

Example for covalently
structure: Diamond cubic

bonded

Compare to covalently bonded

materials Ionic bonded materials
have closed packed structures (
because of the directionality of
covalent bonding)

BONDING AND STRUCTURE

Example of combined
structure: Zircon (ZrSiO4)

bonding

Here there is a covalent

bond

between Si and O ( SiO 4 ) and a

4
ionic bond between this unit and Zr
ion.
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PROPERTIES
Lower density
High melting temperature
Lower thermal conductivity
Low thermal expansion

PROPERTIES
Poor electrical conductivity
Good dielectrics
High hardness and brittle
Good inertness towards chemicals
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PROCESSING
Powder preparation
Shape forming process
Densification or sintering
Final machining

FORMING PROCESS
1. Die pressing
2. Isostatic pressing

3. Extrusion
4. Slip casting
5. Injection moulding

DIE PRESSING
Power mixed with organic binders
Filled into the die
Pressure is applied unidirectional
Inexpensive method

DIE PRESSING
Plunger
Powder
Die

Typical Die pressing setup

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ISOSTATIC PRESSING
Powder mix is loaded into the rubber
mould
Pressed in a hydrostatic moulding
chamber
Density variation is avoided

ISOSTATIC PRESSING
Inlet

Powder
Rubber Mould
Oil
Outlet

Typical setup of Isostatic pressing

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EXTRUSION
Stiff plastic mix (powder+binder) is
extruded through an orifice
Used for making materials having an
axis normal to a fixed cross section

EXTRUSION
Extruded
Component

Piston

Powder
mix

Orifice

Typical setup for Extrusion

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SLIP CASTING
Slip (is a suspension of particle in a liquid
medium) is poured into a plaster - of parries mould
After the
released

drying process the mould is

Slip casting is a simple method and used

to produce complex shapes

SLIP CASTING
Solid Mass

Slip

Plaster Mould

Typical slip casting process

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INJECTION MOULDING
Plastic mix ( power+ thermoplastic
polymer) is preheated in the barrel of
the injection moulding machine.
The viscous material is forced
through an orifice into a shaped tool
cavity.

INJECTION MOULDING
Piston

Orifice

Powder
mix

Tool Cavity

Typical Injection moulding process

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REFRACTORIES
DEFINITION
Refractories are heat resistant
materials
with
high
melting
temperature,
they
are
oxides,
carbides of Si, Al, Zr, Mg, etc
Examples: SiO2, MgO, CaO, ZrO2,
SiC.

REFRACTORIES
Acid refractories
Basic refractories

Neutral refractories

REFRACTORIES
Acid refractories
The refractories which
attacked by acid slags.

are

not

Examples: silica, silicates such as

fire clay, kyanite etc

REFRACTORIES
Basic refractories
The refractories which
attacked by basic slags.
Examples:
Magnesite,
Chrome magnesite, etc

are

not

Dolomite,

REFRACTORIES
Neutral refractories
The refractories which are
attacked by acid or basic slags.

not

Examples: Graphite, Zirconia, Silicon

carbide, etc

REFRACTORIES
FIRE CLAY REFRACTORIES
Raw material is fire clay (grayish or
blackish in colour)

Chemical composition is Al2O3. 2SiO2.

2H2O
It should have refractoriness at least
1650C and be plastic enough to
manufacture bricks.

FIRE CLAY REFRACTORIES

USES
Used in
furnaces.

all

places

of

ordinary

Also used in glass melting furnaces,

pottery kilns, blast furnaces, etc.
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GLASSES(INORGANIC)
DEFINITION
Glass
is
a
noncrystalline,
metastable material, lacks long range
order, which has hardened and
become rigid without crystallizing.
Example of inorganic glasses: Soda
lime glass, fused silica, etc.

GLASSES(INORGANIC)
Glass transition temperature

Glass composition

GLASS TRANSITION TEMPERATURE

For any amorphous materials the critical
temperature which
separates glassy
behavior from rubbery behavior is called
glass transition temperature (Tg).
Tg can be defined using the volume
change associated with heating or
cooling.

GLASS TRANSITION TEMPERATURE

If the cooling rate is slower enough for
crystallization there will be a volume
change associated with melting point (Tm).
If the cooling rate is fast to prevent
crystallization the volume of the material
follows the slope characteristics of liquid
even below melting point (Tm).

GLASS TRANSITION TEMPERATURE

The liquid present below Tm is called
super cooled liquid.
On further cooling of this liquid, at a
particular temperature the slope of
the curve decreases, and this
temperature is called
glass
transition temperature (Tg).

Specific Volume

GLASS TRANSITION TEMPERATURE

Super Cooled
Liquid

Liquid

Glass
Crystal
Tg

Tm Temperature

Volume change as a function of temperature

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GLASS COMPOSITIONS
Most of the glasses have:

Silica (SiO2) ( major constituent)

Lime (CaO)
Soda (Na2O) and
Other Oxides like PbO, B2O3, etc.

GLASS COMPOSITIONS
According to properties oxides are
divided into three types:
Glass (Network) formers
Network modifiers
intermediates

GLASS COMPOSITIONS
GLASS FORMERS
These
oxides
forms
three
dimensional network using its
triangular or tetrahedral units.

Example: SiO2, B2O3, P2O5, V2O3,G2O,

etc.

GLASS COMPOSITIONS
NETWORK MODIFIERS
Oxides incapable of forming a three
dimensional network, but break up
the network structure, thus lowers Tm
and Tg.
Example: Na2O, CaO, Y2O3, etc.

GLASS COMPOSITIONS
INTERMEDIATES
Oxides doesn't form glass by itself
but incorporated in the network
structure of the glass formers.
Example: Pb2O, Al2O3, BeO, TiO2, etc.

GLASS COMPOSITIONS
TYPICAL GLASS COMPOSITION
1. Fused silica ( 99%SiO2)
2. Window glass ( 72%SiO2, 1%Al2O3,
10% CaO, 14%Na2O, 2%MgO)
3. Optical flint (50%SiO2, 1%Na2O,
19%PbO, 8%K2O, 13%BaO)
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POLYMERS
DEFINITION
POLYMERIZATION MECHANISMS
DEGREE OF POLYMERIZATION
TYPES OF POLYMERS

POLYMERS
DEFINITION
Polymers are organic materials,
with long chain molecules, having
carbon as the common element in
their makeup.

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POLYMERS
POLYMERIZATION MECHANISMS
Addition polymerization
Condensation polymerization

ADDITION POLYMERIZATION
Addition polymerization is produced
by covalently joining the individual
molecules,
producing
chains
without changing the chemistry of
the reactants.
No byproduct is produced.

ADDITION POLYMERIZATION
STEPS IN ADDITION POLYMERIZATION

Initiation

Chain propagation

Termination

ADDITION POLYMERIZATION
Reaction is initiated
pressure or a catalyst.

by

heat,

Polymerization is terminated by
collision between the active ends of
two chains or by addition of
terminator (i.e, free radicals from
catalyst)

ADDITION POLYMERIZATION
Chain length is controlled by the
amount of initiator (for small amount
of initiator longer chain length due to
less amount of terminator)
Example: Production of polyethylene
from ethylene ( C2H4)
initiator is Hydrogen peroxide (H2O2)

ADDITION POLYMERIZATION
H

H O O H +C=C
H

Ethylene Molecule

H
H

H O + H O + C C Mer
H

ADDITION POLYMERIZATION
H

HO + HO CC
H

H H

H H

CC CC CC
H

H H

H H

Initiation of
reaction

Polyethylene

H
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CONDENSATION POLY
Two or more molecules joined by a
chemical reaction that releases a biproduct such as water, alcohol, etc.
This mechanism often involves
different monomers as starting
molecules.

CONDENSATION POLY
Example: Dimethyl terephtalate and
ethylene
glycol
to
produce
Polyethylene
terephthalate
(PET
polymer).

By product
(CH3OH)

is

methyl

alcohol

CONDENSATION POLY
H

HCOC
H

COC H
H

+
H

HO C C OH
H

CONDENSATION POLY
H

HCOC

COC C OH

PET
Polymer

H
HCOH
H

CONDENSATION POLY
The length of the polymer chain
depends on the ease with which the
monomers can diffuse to the end and
undergo condensation reaction.
Chain growth ceases when no more
monomer reach the end of the chain.
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DEGREE OF POLY
Polymers do not have a fixed
molecular weight, instead have a
range.
The average length of a linear
polymer, or average number of
repeat unit in the chain is called
degree of polymerization.

DEGREE OF POLY
Degree of polymerization
Average molecular weight of polymer

Molecular weight of repeat unit

Weight average molecular weight

Mw fi Mi

DEGREE OF POLY
Number average molecular weight

Mn X i Mi
Mi mean molecular weight of ith
range.
fi weight fraction of the polymer
having chains within ith range.
Xi fraction of the total number of
chains within ith range.
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TYPES OF POLYMERS
THERMO PLASTICS
THERMOSETTING PLASTICS

ELASTOMERS

THERMOPLASTICS
Composed of long chains, may or
may not have branches.
Bonded together by weak Vander
walls bonds between chains.

THERMOPLASTICS
They
can
crystalline.

be

amorphous

or

Behave in a plastic, ductile manner.

Processed into shapes by heating to
elevated temperatures and can be
recycled.
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THERMOSETTING PLASTICS
Composed of long chains molecules
that are strongly cross linked.
Stronger,
but
thermoplastics.

brittle

than

They do not melt upon heating but

begins
to
decompose,
hence
recycling is difficult.
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ELASTOMERS
They are known as rubbers.
Have elastic deformation > 200%

They can be thermoplastics or lightly

cross linked thermosets.
Polymer has coil-like molecules that can
reversibly stretch by applying force.