CHAPTER V

Structure of ceramics and polymers

• 5.1 Introduction
• Now a days many new materials are
manufactured and extensively used in various
industries .
• The properties of this materials may be
properly understood in terms of molecular
structure.
• Materials are divided in to inorganic and
organic materials besides metallic
materials.
•
fundamentals of material science 1
• Ceramics are inorganic non- metallic materials.
• Many oxides, nitrides carbides fall under the
category of ceramics.
• A great number of different types of ceramic
materials ,such as glasses, clay products,
refractories, abrasives, etc are producing by
processing and or/used at high temperatures.
• A large group of engineering materials of
steadily increasing importance in industrial
applications are of organic nature are natural
any synthetic polymers.
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• Naturally occurring of polymers are derived
from plants and animals .
• These are wood, rubber, wool, leather , etc.
• many of our use full plastics, polyvinylchloride
(pvc), nylon, Teflon, etc. are synthetic
polymers.
• In this chapter, we study the structure of
these materials to understand and evaluate
their properties.

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 5.2.Structure of ceramics
AX-Type Crystal Structures
• AX type crystal structure equal number of cations (A) and
anions (X) base on chemical formula.
• Rock Salt structure unit cell crystal structure is base on FCC
(face–centered cubic).
• Interpenetrating FCC lattice (frame or form).
• Face–centered arrangement of cations (+).
• Face–centered arrangement of anions (–).
• Cation–anion radius ratio (rC / rA) = 0.414–0.732
• Coordination number = 6
• Crystal structure of common ceramic
materials like NaCl (salt), MgO,
MnS,LiF, and FeO.
Unit cell crystal structure of
fundamentals of material science 4
sodium chloride (NaCl).
 AmXp-Type Crystal Structures
• AmXp type crystal structure not equal number of cations
• (A) and anions (X) base on chemical formula.
• m number of cations (+).
• p number of anions (–).
• Example AX2 like CaF2 (flourite)
• Cation–anion radius ratio (rC / rA) = 0.8 (approx.)
coordination number = 8
• Cations (Ca2+) cube center.
• Anions (F–) cube corners.
• Crystal structure of common ceramic
materials like CaF2 , ZrO2 , UO2 ,PuO2 ,
and ThO2 Unit cell crystal structure of
calcium flouride (CaF2).
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 Structure of silica
• Chemically ,the most simple silicate material is
silicon dioxide or silica (siO2) structurally, it is a
3-dimensional net work that is generated
when ever corner oxygen atom in each
tetrahedron is shared by adjacent tetrahedral.

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 AmBnXp-Type Crystal Structures
• AmBnXp type crystal structure more than one type of
• cation (A and B).
• m number of cations (+) type 1.
• n number of cations (+) type 2.
• p number of anions (–).
• Not equal number of cations (A and B) and anions (X) base
• on chemical formula.
• Example BaTiO3 (Barium Titanate) perovskite cubic
• crystal structure (occur at > 120OC).
• 2 Cation types Ba2+ at cube corners
and Ti4+ at cube center
Anions (O2–) cube faces center.
Unit cell crystal structure of
barium titanate
fundamentals (BaTiO3
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 Structure of silicates
• Most ceramic materials contain silicates besides
being cheap and plentiful.
• Possess certain distinct properties which are
useful in engineering applications.
• The most common known silicates is Portland
cement which forms a hydraulic bond for rock
aggregates.
• Brick, tile, glass, and various enamel are also
made of silicates
• Silicates also used as
i. chemical wares
ii. Electrical insulators
iii. Reinforcing glass fibers etc.
fundamentals of material science 8
 Cont…
The various types of silicate structures are
i. silicon-oxygen tetrahedron (SiO4)4-
structure
ii. Double and poly- tetrahedral structures
iii. Chain structures
iv. Sheet structures
v. frame work structures
vi. Vitreous structures
i. Silicate oxygen tetrahedron (SiO4)4-
It is primary structural unit of silicate
fundamentals of material science 9
 Cont…
• In this structure one silicon atom fits interstitially among
four oxygen atoms with ionic covalent bond atoms have
only seven electrons rather than eight available to its
outer most shell.
•Thus to be satisfied, and become stable each oxygen
atom needs one mole electron which is made available by
any of the following two methods.
a) By taking an electron from some other metals
E.g. Mg, Ca, etc
Forsterite (Mg2SiO4), a mineral which is a high
temperature refractory
b) By permitting each oxygen atom to share an electron
pair with a secondfundamentals
silicon of material science 10
 Fig. Silicon –oxygen tetrahedral (SiO4)4-

ii. Double and poly-tetrahedral structures

• The second of the two methods (as
mentioned above) available to over
come the deficiency of electrons from
oxygen produces a double tetrahedral
unit. One of the oxygen is a member of
two units. fundamentals of material science 11
 Cont…
• There fore the composition of double
tetrahedral units ions Si2O7 which produces a
(Si2O7)-6 ions. pyrosilicate is an example of
double tetrahedral structure.
• A poly tetrahedral structure results when three
or more tetrahedral units link together.
• A ring type structure is produced this way. One
of the oxygen is a member of two units.
• The composition of (a three) polyhedral unit is
Si3O9 which produces (Si3O9)6-ions.
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 Fig. Poly-tetrahedral silicate(Si3O9)6-

iii. Chain structure

• The corners of each tetrahedral when linked,
from a chain structure.
• One of the oxygen shared by two adjacent
tetrahedral and similar sharing oxygen takes
place on the other corner of the tetrahedral.

fundamentals of material science 13

 Cont…
•A double chain structure , as in amphiboles
results when two parallel identical chains are
polymerized by sharing oxygen to every
alternate tetrahedron
•The chain structure theoretically, can be
almost infinite in length

Fig. Single chain structure

Fig. Double chain structure
fundamentals of material science 14
 iv. Sheet structure
• A sheet structure results when the double
chain structure extends infinitely in a two-
dimensional plane (Ruther than along a line).
• The structure arrangement provides certain
important properties, eg. The lubricating
characteristics of talc and plasticity of clay,
the cleavage of mica are the consequence of
this structural arrangement.
• the sheet structures is found in ceramic
materials which as clays, micas and talc
fundamentals of material science 15
 Cont’d

Fig. Sheet structure

fundamentals of material science 16

 v. Frame work structure
• An extension of silicate tetrahedral unit in the
three- dimension gives rise to a frame work
structure .
• Where as sheet structure extends in two
dimensional plane, a frame work structure
does so in three-dimensionals
• The frame work structure
a) possess relatively low densities
b) Has low atomic packing factors and
c) Is generally hard
Eg. Quartz, feldspar, cristobilite etc.
fundamentals of material science 17
 vi. Vitreous structure
• Glass is vitreous silicate.
• It is possesses a vitreous structure glass is a
three dimensional frame work structure
containing covalent bond.
• Glasses vivid (vitreous) form of silicate (glass)
in two dimensional as shown in fig

Fig. Vitreous structure

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 polymers
• Introduction
A polymer is composed of a large member of
repetitive called monomers or simple molecules.
Thus a polymer is made up of thousands of
monomers joined chemically together to form a
large molecule.
It has be observed that each molecules of a
polymer is either a lone chain or a net work of
repetitive units or monomers.
fundamentals of material science 19
 Classification of polymers
• Polymers are broadly classified as
i. Thermoplasts, and
ii. Thermosets
Depending on behavior with a change in
temperature
A thermoplastic is a polymer that turns to a liquid
when heated and freezes to a very glassy state
when cooled sufficiently.

fundamentals of material science 20

 Cont…
• Most thermoplastics are high-molecular-
weight polymers whose chains associate
through weak Van der Waals forces
(polyethylene); stronger dipole-dipole
interactions and hydrogen bonding (nylon).
• Thermoplastic polymers differ from
thermosetting polymers (Bakelite, vulcanized
rubber) since thermoplastics can be remelted
and remolded.

fundamentals of material science 21

 Thermosets
• have a three dimensional net of primary
bonds, as polymerization proceeds in all
directions in their case.
• plastics when heated, will chemically
decompose, so they can not be recycled.
• Yet, once a thermoset is cured it tends to be
stronger than a thermoplastic.
• Typically, linear polymers with minor branched
structures (and flexible chains) are
thermoplastics.
• The networked structures are thermosets.
fundamentals of material science 22
• Long chain polymers can be subdivided in to
three parts
i. plastics
ii. Fibers
iii. elastomers
Structure of long chain polymers
The formation of long chain polymer starting
from a monomer is easily understood by
considering the ethylene molecule which has

fundamentals of material science 23

 Cont…
a bond necessary for chain formation.
During the polymerization, the double bond is
opened up in to single bond.

fundamentals of material science 24

 Cont…
• The monomers are bonded together end to
end in a polymerization reaction.

In the bond representation each

Tetrahedral
carbon atom is tetrahedrally arrangement of
C-H

bonded to four
neighbors with
bond angle of 109.50
fundamentals of material science 25
 Ethylene based a long chain polymers
name Monomer structure USES
R1 R2 R3 R4
Polyethylene H H H H Sheets, tubes and containers
(polypthene)
PVC H H H Cl Construction, rigid pipe, flooring, wire and
cable insulation, film, sheet
Poly propylene H H H CH3 Automobile and appliance parts, rope,
cordage, webbing, carpeting, film
Polymethylmeth H H CH3 COOCH3 Transparent windows and fixtures
a-cylate
Polystylne H H H C6H5 Foam and film packaging, foam insulation,
appliances, house wares, toys
PTFE (Teflon) F F F F coating in frying pans razors, bearings,
chemical ware
Polyacylonitile H H H cN human body implants as substitute in
(orlon) clothings
fundamentals of material science 26
 Crystallinity in long chain Polymers
Ordered atomic arrangements
involving molecular chains
Crystal structures in terms of unit
cells
Example shown
- polyethylene unit cell
– Polymers can be crystalline
(i.e. have long range order)
– However, given these are
large molecules as compared
to atoms/ions
(i.e. metals/ceramics) the
crystal structures/packing will
be much more complex
fundamentals of material science 27