STRUCTURES OF

CERAMICS
REFF:
Materials Science & Engineering; An Introduction
Callister, W. D, Jr, 2007, John Wiley & Sons
Fundamental of Ceramics, Barsoum, M. W., 2003,
McGraw-Hill
Engineering Materials 2; An Introduction to
Microstructures, Processing and Design, Ashby, M. F and
Jones, D. R. H, 1986, Pergamon Press

Introduction
CERAMICS: Greek keramikos = burn
stuf
solid compounds formed by heat (&/P)
applications followed by cooling
desirable properties are achieved
through high-T process (firing)
Firing causes irreversible
transformation resulting a material that
has lost its plasticity & no longer
capable to rehydrate
at least 2 elements; 1 is a non-metal,

Ionic Vs Covalent
Bonding
IONIC
BONDING
When more than one type of atoms are present in a material,
one atom may donate its valence electrons to a diferent
atom, filling the outer energy shell of the second atom. Both
atoms now have filled/emptied outer energy levels, but both
have acquired an electrical charge and behave as ions.
The atom that contributes the electrons is left with a net
positive charge and is called a cation, while the atom that
accepts the electrons acquires a net negative charge and is
called an anion.
The oppositely charged ions are then attracted to one
another and produce the ionic bond.

 Occured by transfer electron;

form between very active metallic & nonmetallic
elements
Atomsof a metallic element easily give up their
valence electrons to the nonmetallic atoms
to form AX ionic bonding, A loses e easily, X
accepts e without too much energy input
Ionic bonding is termed nondirectional the
magnitude of the bond is equal in all directions
around an ion
It follows that for ionic materials to be stable, all
positive ions must have as nearest neighbors
negatively charged ions in a three dimensional
scheme, and vice versa
The predominant bonding in ceramic materials is
ionic.
For N valence electrons, an atom can covalently
bond with other atoms 8 N

COVALENT BONDING
the sharing of covalent bonding electrons between adjacent atoms.
Two atoms will each contribute at least one electron to the bond, and
the shared electrons may be considered to belong to both atoms.
forms when atoms have the same electronegativity combine
energies of bonding electrons of A & X are comparable
If the electron energy of the atoms is diferent transfer energy (ionic
bonding)
Each instance of sharing represents one covalent bond
e.g: silicon atom, has a valence of four, obtains eight electrons in its
outer energy shell by sharing its electrons with four surrounding silicon
atoms each silicon atom is bonded to 4 neighboring atoms by 4
covalent bonds
Many nonmetallic elemental molecules (H2, Cl2, F2 etc) as well as
molecules containing dissimilar atoms, such as CH4,H2O, HNO3, and
HF, are covalently

valence
The number of covalent bonds is
determined by the number of valence
electrons
The valence of an atom is the number of
electrons in an atom that participate in
bonding or chemical reactions.
The valence of an atom is related to the
ability of the atom to enter into chemical
combination with other elements
Usually, the valence is the number of
electrons in the outer s and p energy
levels.
Examples of the valence are:

It is possible to have interatomic bonds that are partially ionic

and partially covalent
the degree of either bond type depends on the relative
positions of the constituent atoms in the periodic table or the
diference in their electronegativities.
Electronegativity (e greed) the tendency of an atom to gain
an electron; the power of atom to attract electrons to itself
Atoms with almost completely filled outer energy levelssuch
as chlorineare strongly electronegative and readily accept
electrons.
However, atom with nearly empty outer levelssuch as
sodiumreadily give up electrons and have low
electronegativity.
The wider the separation (both horizontallyrelative toGroup
IVAand vertically) from the lower left to the upper-right-hand
corner (i.e.,the greater the diference in electronegativity)
the more ionic the bond.
Conversely, the closer the atoms are together (i.e., the smaller
the diference in electronegativity), the greater the degree of
covalency.
If the electronegativity diference between them (x)is large

 Characteristics of ions which afect crystal structure:

1. magnitude of electrical charged of each ions
Crystal electrically neutral
(+) charges must be balanced by an equal number of ()
chemical formula indicates ratio of + to
Ex CaF2 calcium ions (+2) & fluoride (-)
2. relative size of + and ion
Involve size/ionic radii (rc & ra)
Metalic elements give up electrons when ionized
cations are smaller than anions rc/ra <1
Each cation prefers as many neighbour anions, anions also
desire a maximum number of cation.

Stable structures require that cations and anions are in

touch

Coordination number
the number of atoms touching a particular atom, or
the number of nearest neighbors for that particular
atom.
number of anions neighbors for a cation) related
to rc/ra
This is one indication of how tightly and effisiently
atoms are packed together.
For ionic solids, the coordination number of cations
is defined as the number of nearest anions.
The coordination number of anions is the number
of nearest cations.

 Table: Coordination
numbers and
geometries for
various rc/ra
red cation
whte anion
Common
coordination
numbers for
ceramic: 4, 6 and 8
rc/ra>1
coordinate no. 12

The size of an ion depend several factors,

e.g:
1. coordination number
Ionic radius increase as the number of
opposite charge neighbor ions increases
ionic radii for (coord no. 4<6<8)
2. charge on an ion
Removing e from atom/ion, the remaining
valence electrons become more tightly
bound to the nucleus decrease ionic
radius
Ionic size increases when electrons are
added to an atom or ion
Radii for Fe: Fe2+: Fe3+ = 0.124: 0.077:

Atom arrangement
1 unit cell: the smallest group of
atoms form a repetitive pattern in
describing crystal structure
represent crystal stucture

 Types of atomic or ionic arrangements:

1.No Order
These materials randomly fillup whatever space is
available to them.
In monoatomic gases, such as argon (Ar) atoms or ions
have no orderly arrangement.
2. Short-Range Order (SRO)
A material displays short-range order (SRO) if the special
arrangement of the atoms extends only to the atoms
nearest neighbors
Amorphous/glassy/non crystalline material; e.g. glass
3. Long-Range Order (LRO)
the special atomic arrangement extends repeat periodicity
>>bond length
over much larger ~>100 nm up to few cm
The atoms or ions in these materials form a regular
repetitive, gridlike pattern, in three dimension
crystalline materials; e.g. ceramics

Non crystalline solid

lack a systematic and regular arrangement

rangement of atoms over relatively large atomic
distances.
also called amorphous or supercooled liquids,
inasmuch as their atomic structure resembles that
of a liquid.
Whether a crystalline or amorphous solid forms
depends on the ease with which a random atomic
structure in the liquid can transform to an ordered
state during solidification
An amorphous condition may be illustrated by
comparison of the crystalline and noncrystalline
structures of the ceramic compound silicon dioxide
(SiO2), which may exist in both states.

Crystal structure

based on the unit cell geometry only.

Within this framework, an x, y, z coordinate system is
established with its origin at one of the unit cell corners;
each of the x, y, and z axes coincides with one of the three
parallelepiped edges that extend from this corner.
The unit cell geometry is completely defined in terms of six
parameters: the three edge lengths a, b, and c, and the
three interaxial angles a, , and .
These seven crystal systems are cubic, tetragonal,
hexagonal, orthorhombic, rhombohedral (also called
trigonal), monoclinic, and triclinic
The cubic system, for which a = b = c and a = = = 90 ,
has the greatest degree of symmetry. Least symmetry is
displayed by the triclinic system, since a b c and a
.

Single crystal
when the periodic and repeated arrangement of
atoms is perfect or extends throughout the
entirety of the specimen without interruption, the
result is a single crystal.
All unit cells interlock in the same way and have
the same single crystal orientation.

Polycrystalline material

A polycrystalline material is comprised of many crystals

with varying orientations in space. These crystals in a
polycrystalline material are known as grains.
The borders between tiny crystals, where the crystals are in
misalignment and are known as grain boundaries.
Stages in the solidication of a polycrystalline:
Initially, small crystals or nuclei form at various positions.
These have random crystallographic orientations. The small
grains grow by the successive addition from the
surrounding liquid of atoms to the structure of each. The
extremities of adjacent grains impinge on one another as
the solidification process approaches completion.

Type of crystal structure

AX: structure of NaCl, CsCl, ZnS
AmXp
AmBnXp

AX-type crystal structures

equal number of A (cation) & X (anion)

Referred as AX
3 structures: rock salt, CsCl and ZnS
Ionic & or covalent bonding
Ionic MgO; 2 e of A transferred to X, result in Mg2+
& O2 Covalent ZnS; sharing elektron

Rock salt (NaCl) structure

The most common AX
crystal structure
Electrostatic attraction
between Na+ & Cl- hold the
crystal together
Max. electrostatic
interaction each Na+ has
6 Cl-, no Na+ neighbours
(vice versa)
Coordination number for
both + & - is 6 (octahedral)
1 unit cell generated
from FCC of anion with 1
cation in cubic center & 1 at
centered of each of 12 cube

Cesium cloride (CsCl)

stucture
Coordination number
for both ions is 8
(cubic)
The anions are at each
of the corners of a cube
Single cation is at the
cube center
This structure is
possible when the
anion and the cation
have the same valence

Zinc Blende (ZnS) structure

Coordinate number for
both ions is 4
(tetrahedral)
all corner and face
positions of the cubic
cell are occupied by S
atoms
the Zn atoms fill
interior tetrahedral
positions
Each Zn atom bonded
to 4 S atoms, vice
versa
Most often the atomic
bonding is highly
covalent

AmXp Type crystal

structures
Charges of + & - are
not the same, m p
Example: AX2 CaF2
Ca ion at the centers of
cube, F ion in the
corner
1 unit cell consists of 8
cubes

AmBnXp Type crystal

structure
2 types of cation, A & B
Chemical formula
AxBnXp
Ex. BaTiO3
Ba2+ ions are situated
at all 8 corners of the
cube, single Ti4+ is at
the centre, O2- ions is at
the centre of 6 faces

SILICATE CERAMIC
Silicates are composed primarily of silicon and
oxygen, abundant elements in earths crush; soil,
rock, clay
Each silicon atom bond strongly to 4 oxygen atom
Basic unit in all silicates tetrahedron (oxygen
are situated at the corners, oxygen is at the
centre)

silica
The most simple: silicon
dioxide/silica
Pure silica no metal ions,
every oxygen becomes a
bridge between 2 silicon atoms
Every corner oxygen atom is
shared by adjacent tetrahedra
The materials electrically
neutral, all atoms have stable
electronic structures
Ratio Si to O 1:2 (indicated
by chemical formula)
If tetrahedras are arranged in a
regular & order crystalline
3 polymorphic: quartz,
cristobalite & tridymite

The silicates

Silica Glasses

Noncrystalline solid or
glass, high randomness
Fused silica/vitreous
silica
Basic unit tetrahedron
(same as the
crystalline)
Pure silica forms glass
with high softening T
(1200 C)
Great strength and
stability, low thermal
expansion but
hardtosilica
Commercial
glasses
work with
high
glasses
add because
with other
metal
in
viscosity
oxide to reduce viscosity
E.g. CaO, Na2O add positive
ion to the structure &break up
the network network
modifiers
Add 1 Na2O molecules
introduces 2 Na+, each

GLASS & CERAMIC

SHAPING & FORMATION

GLASS & GLASS CERAMICS

Glass Properties:
Upon cooling, a glass
continues to be more
viscous with decreasing
temperature
no definite temperature at
which the liquid transforms
to a solid
volume decreases
continuously with
temperature reduction
TgThe temperature at
which the transition in the
amorphous regions
between the glassy and

Crystal discountinue
decrease in vol at Tm
Tg: glass transition T
Tm: melting T for crystalline

Glass Forming
Heat RM to an elevated temperature above which
melting occurs
Most commercial glasses are of the silicasoda
lime variety
silica (quartz)Na2O(soda ash, Na2CO3)
CaO(limestone, CaCO3)
Important: homogeneous and pore free
Homogeneity complete melting and mixing of
RM
Porosity results from small gas bubbles that are
produced these must be absorbed into the melt
or otherwise eliminated, which requires proper
adjustment of the viscosity of the molten material
4 methods to fabricate glass: pressing, blowing,
drawing & fiber forming

pressing
relatively thick-walled pieces (plates
and dishes.
The glass piece is pressed in a graphitecoated cast iron mold with desired shape
the mold is heated to ensure an even
surface.

BLOWING
some glass blowing is
done by hand art
object
RM press in mold
parison (temporary
shape); place into
finishing or blow mold
& forced to conform
to the mold contours
by the pressure
created from a blast
of air

DRAWING

Form long glass pieces (sheet, tubing, rod etc)

hot rolling may applied
Flatness & surface finish may be improved by floating
the sheet on a bath of molten tin at high T followed
slowly cooled and subsequently heat treated

Clay Products
Clay are aluminosilicates Al2O3 & SiO3
contain chemically bound water
Broad in physical characteristic, chemical
composition, structure
Impurities: oxide of Ba, Ca, Na, K, Fe
May contain nonplastic ingredient
Nonclay minerals: flint, quartz, feldspar
Quartzrelatively hard, little change in
high T, ability to form glass

Composition
contain mineral
Clay minerals play 2 roles:
1.When added water, form
hydroplasticity
2.Fuse or melt over a range T
dense & strong ceramic during
firing without complete melting;
desired shape
Common clay mineral: kaolinite
(Al2(Si2O5)(OH)4
Most prevailing structure layer
structure
When water is added, the water
molecules fit in between these
layered sheets and form a thin film

Binder & plastiziser

Binder a component that is added to hold the
powder together while shaping the body
2 functions of binder: 1) provide plasticity
necessary for forming & 2) provides the dry
(green) shape with strength sufficient to survive
the handling process between shaping and
sintering
requirements for the binder is able to be
eliminated from the compact during the firing
process without any disruptive efect water,
polymers
Poly (vinyl alcohol) (PVA high green strength)
and poly (ethylene glycol) (PEGhigh green
density) are the two of the most popular binders

Plastic forming
Plasticizer is the component of a binder that keeps it
soft or pliable; it improves the rheological properties
Mixing ceramic powder with large vol of liquid to
produce a mass that deformable/plastic under P
The binder: water, organic liquid, complex comp to
achieve required viscosity & properties
NOTE
Slurry a suspension of ceramic particles in a
liquid
Green state ceramic compact that is strong
enough to be handled and machined but is not fully
dense and the bonds between the grains are not
strong.

Slip & slurry

slip consists of fine (<10 m) cceramic powder
particles that are suspended in a fluid usually
water.
a solid content up to ~60 vol%.
Deflocculents are added to the slip to modify the
electrical properties of each particle (the particles
repel each other)
deflocculation process by which floccules
present in a liquid break up into fine particles
producing a dispersion
Defloculation >< coagulation
a deflocculant an additive that causes this

CERAMIC SHAPING
3 methods in ceramic shaping:
Powder compaction: dry pressing, hot pressing,
cold isostatic pressing, etc
casting: using a mold with the ceramic as or
containing of liquid or slurry
Plastic forming: using pressure to shape the
green ceramic; extrusion, injection molding etc.

Powder compaction
Pressing of free flowing powder
Pressure application depends on final product
2 types: dry pressed (i.e. without addition of
binder) & pressed with the addition of suitable
binder
uniaxially simple shape, or isostaticcally
complex shape

Dry pressing

three basic steps: filling the die, compacting the

contents, and ejecting the pressed solid
A particle size 20 and 200 m; a high volume
fraction of small particles s problems with flow and
sticking of the punches.
During pressing the powder particles must flow
between the punches uniformly filled.

 bottom punch is in the low position a cavity the

cavity is filled with free flowing powder ; the
powder is struck of level with the top of the die.
The top punch descends and compresses the
powder either to a predetermined volume/set
pressure.
After pressing, both punches move upward The
compact is then ejected

Hot pressing
Pressing performed at high temperatures
The die assembly is contained within a high
temperature furnace
During hot pressing the ceramic powders may sinter
together to form a high-density component.
the ADVANTAGES of this process:
1 The powder does not have to be of the highest
quality.
2 Large pores that are caused by non uniform mixing
are easily removed.
3 densify at temperatures lower (typically half the
melting temperature of the material) than those
needed for conventional pressure less sintering.
4 densify covalently bonded materials such as B4C, SiC,

 DISADVANTAGE :
1 Die for high T is
expensive and do not
generally last long.
2 limited simple shape:
flat plates, block,
cylinder

Graphite is the most

widely used die
material (up to 2200C,
10 - 30 Mpa)
Graphite properties:
1 easy to machine
2 cheap
3 strength increase with T
4 good creep resistance
5 excellent thermal
conductivity
6 low coef of thermal
expansion

Cold isostatic pressing-CIP

apply of hydrostatic pressure to a powder

in a flexible container.
The advantage of applying pressure in all
directions more uniform compaction of
the powder and more complex shapes
Can be performed either with or without
applied heat.
WET BAG CIP PROCESS
ADVANTAGES:
Wide range of shapes and sizes can be
produced
Uniform density of the pressed product
Low tooling costs
DISADVANTAGES:
Poor shape and dimensional control
(particularly for complex shapes)
Long cycle times (typically between 5 and

Casting ceramic
In Tr, require slurry ceramic powder
particles to be suspended in a liquid
2 type: slip casting & tape casting
S lip casting slurry is poured into porous
mold that remove the liquid, leave a
particulate compact in the mold
Tape casting to make thick film/sheet

Slip casting
The slip is poured into a mold (usually
plaster of Paris-2CaSO.4H2O) that has
been made by casting round a model of
the required shape
The mold allow for the shrinkage of the
cast ceramic on drying and sintering.
The fineness of the powder (in the slip)
and the consequent high surface area
ensure that settling does not occur.
Na silicate (or soda ash) is added to the
slip to deflocculate the particles. The
water passes, via capillary action, into
the porous plaster leaving a layer of the
solid on the wall of the mold. Once a
sufficient thickness has been cast, the

 Drain slip casting the processs

terminated when desired thickness
reached, pour out the excess slip.
After dried, the mold is disassembled
Characteristic the Slip high specific
gravity, very fluid & pourable
sanitary lavatory ware, art objects

 Slip casting is a low cost way to produce complex

shapes
method for the production of teapots, jugs, and large
articles (whitewares)
One of the t signs of slip casting ceramic is that it is
hollow.
Another variant of the slip casting process is solid/tape
casting slip is continually added until a solid cast is
made. These items will not be hollowrelatively, they
will be heavier.
Characteristic slip: high specific gravity, very fluid,
pourable (depend on solid to water ratio), free of
low drying
shrinkage
bubble,
Solid casting
water
from slip&ishigh strength
Mold
properties
mold
quality
of casting
absorbed
into the
when
Usually
paris
ecomonical,
easy to
poured, plaster
leavingof
solid
layer
on the
fabricate, reusable
mold wall (thickness, f=(t))
May continue until entire mold
cavity becomes solid

extrusion
Extrusion involves forcing a
deformable mass through a
die orifice (like toothpaste
from a tube)
widely used to produce
ceramic components having
a uniform cross section and a
large length-to-diameter
ratio such as ceramic tubes
and rods
Extrusion is also used to
produce the alumina shells
for sodium vapor lamps and

Injection molding

Used for ceramic powder which is added to a thermoplastic

polymer.
the polymer is usually referred to as the binder
The ceramic powder is added to the binder and other organic
materials to provide a mass that has the desired rheological
properties
The plastic mass is first heated, at which point the
thermoplastic polymer becomes soft and is then forced into a
mold cavity. The heated mixture is very fluid and is not selfsupporting (this is diferent from the situation encountered in
extrusion). The mixture is allowed to cool in the mold during
which time the thermoplastic polymer hardens.
ADVANTAGES:
usedare
to fabricate
complex
shapes
retained with very little distortion during
ceramic
components
withdensities,
complex although low, are uniform.
sintering
since the

shapes; cycle times can be rapid

high-volume process.
DISADVANTAGES: initial tooling
costs is quite high

Drying & Firing

Ceramic formed hydroplastically/slip
casting significant porosity &
insufficient strength, contain some liquid
added in previous operation
Remove by drying green body
Continued with firing
Defect may be introduced results of
nonuniform shrinkage

drying
early stage, clay particles surrounded &
separated by thin water film
Drying: remove some liquid remain interparticle
separation decrease (shrinkage);
Critical to control the rate of water removal
Drying interior is accomplished by difusion of
water molecules to surface where evaporation
occurs
Rate of evap>difusion surface will dry faster
than interior shrink
Nonuniform shrinkage & defect formation thick
>thin pieces
More water content more extensive the
shrinkage; kept as low as possible
Particle size decrease shrinkage increase

Binder burnout

removal of water from the shaped clay.

The rest of the firing process causes structure changes and
transformations in the silicate itself.
Expected remove binder without cracking or distorting
the ceramic compact.
Binder burnout forms defects in the processing of a
ceramic: macroscopic defects, such as cracks and blisters
afect the mechanical strength and other properties.
In commercial ceramic which often consists of several
components challenging to be controlled, diferent boiling
points and decomposition temperatures.
The components with low boiling points (e.g., waxes)may
be removed by evaporation at fairly low temperatures.
The process of binder removal is kept slow to redue
possibility of macrodefects being produced.

firing
Fire between 900-1400 C (RM
composition & desire properties)
During firing operation density
increase (porosity decrease) &
mechanical strength enhance
Complex reactions occured
vitrification: gradual liquid glass
formation that flows into & fills pore
volume ; f=(T, t, composition);
accompanied by shrinkage
Degree of vitrification controls ceramic
properties (strength, durability &
density)
Addition of fluxing agent reduce T of
liquid phase
Upon cooling, this fused phase forms in
a dense, strong body
Complete vitricifation is avoided

IMPERFECTIONS & APPLICATION

OF CERAMIC

Point defect
Point defects are localized disruptions in an otherwise
perfect atomic or ionic arrangements in a crystal
structure.
may be introduced by movement of the atoms or ions
when they gain energy by heating, during processing of
the material or by introduction of other atoms.
The distinction between an impurity and a dopant :
Impurities element/compounds that are present from
raw materials or processing (e.g. Si single crystals contain
oxygen as an impurity)
Dopants elements/compounds that are deliberately
added, in known concentrations, at specific locations in
the microstructure, with an intended beneficial efect on
properties or processing (e.g. P & B are added to Si
crystals to improve or alter the electrical properties of
pure silicon

Imperfections in ceramics
crystalline defect a lattice irregularity having
one or more of its dimensions on the order of an
atomic diameter
The simplest of the point defects is a vacancy, or
vacant lattice site
A vacancy is produced when an atom or an ion is
missing from its normal site in the crystal
structure

Interstitial defect
An interstitial defect is formed when an extra
atom or ion is inserted into the crystal structure
at a normally unoccupied position
Interstitial atoms or ions, although much smaller
than the atoms or ions located at the lattice
points, are still larger than the interstitial sites
that they occupy.
Consequently, the surrounding crystal region is
compressed and distorted.
Interstitial atoms such as hydrogen are often
present as impurities; whereas carbon atoms are
intentionally added to iron to produce steel.
Unlike vacancies, once introduced, the number of
interstitial atoms or ions in the structure remains

Substitutional Defects
introduced when one atom or ion is replaced by a
diferent type of atom or ion
occupy the normal lattice sites.
may either be larger than the normal atoms or ions, in
which case the surrounding interatomic spacings are
reduced, or smaller causing the surrounding atoms to
have larger interatomic spacings.
alter the interatomic distances in the surrounding
crystal.
introduced either as an impurity or as a deliberate
addition
once introduced, the defects is relatively temp.
independent
Examples dopants such a (P) or boron (B) into Si.
Whether atoms or ions go into interstitial or

 Atomic defects involving host atoms

for each ion vacancies & interstitial are
possible
since ceramic materials contain ions of at least
two kinds (+ & -), defects for each ion type may
occur
NaCl : Na & Cl each interstitials & vacancies
highly improbable that there would be
appreciable concentrations of anion (Cl)
interstitials.
The anion is relatively large, and to fit into a
small interstitial position, substantial strains on
the surrounding ions must be introduced.

 Because the atoms exist as charged ions, when

defect structures are considered, conditions of
electroneutrality must be maintained.
Electroneutrality the state when there are
equal numbers of positive and negative charges
from the ions.
consequently, defects in ceramics do not occur
alone
in AX materials, defect is a cation vacancy anion
vacancy pair known as a Schottky defect
created by removing one cation and one anion
from the interior of the crystal and then placing
them both at an external surface.
Since both cations and anions have the same
charge, and since for every anion vacancy there
exists a cation vacancy, the charge neutrality of
the crystal is maintained

 Defect of a cationvacancy and a cationinterstitial pair

a Frenkel defect
formed by a cation leaving its normal position vacant and
moving into an interstitial site.
There is no change in charge because the cation maintains
the same positive charge as an interstitial.

 The ratio of cations to anions is not

altered by the formation of either a
Frenkel or a Schottky defect
If no other defects are present, the
material is said to be stoichiometric.
Stoichiometry as a state for ionic
compounds wherein there is the exact
ratio of cations to anions predicted by
the chemical formula.
For example, NaCl is stoichiometric if
the ratio of Na+ ions to Cl ions is
exactly 1:1.
A ceramic compound is
nonstoichiometric if there is any
deviation from this exact ratio

 Nonstoichiometry may occur for some ceramic

materials in which two valence (or ionic) states
exist for one of the ion types.
Iron oxide (FeO) can be present in both Fe2+ and
Fe3+ states; depends on temperature and the
ambient oxygen pressure.
The formation of an Fe3+ ion disrupts the
electroneutrality of the crystal by introducing an
excess +1 charge, which must be ofset by some
type of defect.
This may be accomplished by the formation of
one Fe2+ vacancy (or the removal of two positive
charges) for every two Fe3+ ions that are formed
The crystal is no longer stoichiometric because
there is one more O ion than Fe ion; however, the
crystal remains electrically neutral.

Impurities in ceramics
Type: solid solutions of both substitutional and
interstitial
For an interstitial, the ionic radius of the
impurity must be relatively small in
comparison to the anion.
A substitutional impurity will substitute for the
host ion (c/a) to which it is most similar in an
electrical sense:
if the impurity atom normally forms a cation
in a ceramic material, it most probably will
substitute for a host cation.
For example, in NaCl, impurity Ca2+ and O2
ions would most likely substitute for Na+ and
Cl ions, respectively.

 To achieve any appreciable solid solubility of

substituting impurity atoms, the ionic size and
charge must be very nearly the same as those of
one of the host ions
For an impurity ion having a charge diferent
from the host ion for which it substitutes, the
crystal must compensate for this diference in
charge so that electroneutrality is maintained
with the solid.
One way this is accomplished is by the formation
vacancies or interstitials of both ion types

APPLICATIONS

Glasses
The glasses are a familiar
group of ceramics; e.g.
containers, lenses, window
and fiberglass
Non crystalline silicates
with other oxide (e.g. CaO,
Na2O, K2O & Al2O3)
influence the glass
properties.
A typical sodalime glass
consists of approximately
70 wt% SiO3, the balance
being mainly NaO (soda)
and CaO (lime)

Glass Ceramics
Glass can be transformed to crystalline by
high T heat treatment crystallisation
Product: glass-ceramics (fine-grained
polycrystalline)
Process involves nucleation & growth
stage
A nucleation agent (frequently TiO2) is
addded to promote crystallization;
Commonly used as ovenware, tableware,
oven window etc

Clay Products
Very popular products (abundant, inexpensive,
easy to be formed)
Contain nonplastic ingredient which afect the
change that take place during the drying and
firing processes the characteristics of the
finished piece
two broad classifications: the structural clay
products and the whitewares.
Structural clay products include bricks, tiles, and
sewer pipesapplications in which structural
integrity is important.
whiteware ceramics become white after the hightemperature firing group are porcelain, pottery,
tableware, china, and plumbing fixtures, sanitary

Refractories
Properties: the capacity to withstand high
temperatures without melting or decomposing,
endure at high T, capacity to remain inert in
severe enviroment, provide thermal insulation
Common product bricks
Application: metal refining, glass manufacturing,
metallurgical heat treatment, power generation
the performance of a refractory ceramic, to a
large degree, depends on composition.
there are several classifications:

 For many commercial materials, the raw

ingredients consist of both large and fine
particles, which may have diferent compositions.
Upon firing, the fine particles normally are
involved in the formation of a bonding phase,
which is responsible for the increased strength of
the brick
The service temperature is normally below that at
which the refractory piece was fired.
the optimum porosity depends on the conditions
of service.

 Porosity is one microstructural variable

that must be controlled to produce a
suitable refractory brick. Strength, loadbearing capacity, and resistance to attack
by
corrosive materials all increase with
porosity reduction.
At the same time, thermal insulation
characteristics and resistance to thermal
shock are diminished.

Abrasives
used to wear, grind, or cut away
other material, which necessarily
is softer.
Properties: hardness/wear
resistance, tough
Diamond; silicon carbide, tungsten
carbide, aluminium oxide, silica
sand, diamonds
used in several forms: 1) bonded
to grinding wheels, 2) as coated
abrasives, and 3) as loose grains.

 In the first case, the abrasive particles are

bonded to a wheel by means of a glassy
ceramic or an organic resin
Coated abrasives are those in which an
abrasive powder is coated on some type of
paper or cloth material; sandpaper is
probably the most familiar example. Wood,
metals, ceramics, and plastics are all
frequently ground and polished using this
form of abrasive.
Grinding, lapping, and polishing wheels
often employ loose abrasive grains that
are delivered in some type of oil- or waterbased vehicle.

Cements
cement, plaster cement of paris, and
lime
Characteristic: form paste when
mixed with water subsequently set &
hardens
act as a bonding phase that
chemically binds particulate
aggregates into a single cohesive
structure at Tr
the role of the cement is similar to
that of the glassy bonding phase that
forms when clay products and some
refractory bricks are fired
The properties of portland cement,

STRUCTURE OF POLYMERS

 Poly & mers Greek ; meros=part;

polymer=many parts
Natural polymer derived from animals & plants
wood, rubber, cotton, wool, leather, and silk
Other natural polymers such as proteins, enzymes,
starches, and cellulose
this group of materials and the development of
numerous polymers synthesized from small
organic molecules.
Many of our useful plastics, rubbers, and fiber
materials are synthetic polymers.
It can be produced inexpensively, and their
properties can be managed to the degree that
many are superior to their natural counterparts.
In some applications metal and wood parts have
been replaced by plastics that have satisfactory
properties and may be produced at a lower cost.
Most of polymers are organic in origin & based on

Hydrocarbon - HC
HC Intramolecular bonds are covalent
Each C atom has 4 e to participate in
covalent bonding, every H has 1 bonding e
Single covalent bondeach of 2 bonding
atoms contributes 1 e; CH4
Double & triple bond 2 C atoms share 2
& 3 pairs of e; C2H4
Saturated HC all single bond
No new atom may be joined without
removal of atoms that are already bonded
Double & triple covalent bonds
unsaturated;
each C is not bonded to max atoms
other atoms are possible to be bonded to
the molecule

 Some of the simple

hydrocarbons belong to the
paraffin family;
the chainlike paraffin
molecules include methane
(CH4), ethane (C2H6), propane
(C3H8), and butane (C4H10)
The covalent bonds in each
molecule are strong, but only
weak hydrogen and van der
Waals bonds exist between
molecules, and thus these
hydrocarbons
have relatively low melting and
boiling points.
HC comp with same
composition but diferent

Polymer molecules
Large molecule built up by repetition of
small, simple chemical units
Because of their size macromolecules
Atomsre bound by covalent bonds
For C polymer C the backbone
Many times each carbon atom singly bonds
to two adjacent carbons atoms on either
side
2 remaining valence of C may involve in
side-bonding with atoms/radical that are
positioned adjacent to the chain

 C2H4-ethylene (P&Tr) gas

If the ethylene gas is reacted under appropriate
conditions, it will transform to polyethylene (PE),
which is a solid polymeric material.
This process begins when an active center is
formed by the reaction between an initiator or
catalyst species (R*) the ethylene monomer, as
follows:
R*+C2H4 R-C*2H4
The polymer chain then forms by the sequential
addition of monomer units to this active growing
chain molecule. The active site, or unpaired
electron (denoted by *), is transferred to each
successive end monomer as it is linked to the
chain. This may be represented schematically as

 The final result, after the addition of many

ethylene monomer units, is the polyethylene
molecule;

This polyethylene chain structure can also be

represented as

Here the repeat units are enclosed in

parentheses, and the subscript n indicates the

 The vinyl chloride monomer

is a slight
variant of that for ethylene, in which one of the four H
atoms is replaced with a Cl atom.
Its polymerization is represented as

Some polymers may be represented using the following

generalized form:

where the R depicts either an atom [i.e., H or Cl, for

polyethylene or poly(vinylchloride), respectively], or an
organic group such as CH3,C2H5, and C (methyl, ethyl,
and phenyl). For example, when R represents a CH
group, the polymer isvpolypropylene (PP).

 The molecules are composed of structure

called repeat units (Mers)
Monomer: small molecule from which a
polymer is synthesized

 When all of the repeating units are the same

homopolymer
Chain may be composed of 2 or more diferent
repeat units copolymer
Ex: General N-alkane HC
Higher MW increase viscosity

MOLECULAR WEIGHT

Extremely large molecular weights are observed in

polymers with very long chains.
During polymerization process, not all polymer chains
grow the same length
Result in distribution of chain length/MW length
Ordinarily,an average molecular weight is specified
the melting or softening temperature increases with
increasing molecular weight
At Tr polymers with very short chains (M ~100 g/mol)
liquid; ~ 1000 g/mol are waxy solids (such as paraffin
wax) and soft resins; Solid polymers (sometimes termed
high polymers), commonly have M ranging 10,000 several million g/mol)
Thus, the same polymer material can have quite diferent
properties if it is produced with a diferent molecular
weight.
There are several ways of defining average molecular

1)The number-average MW

Dividing the chains into

series of size range
then determining the
number fraction of chain
within each size range.
Expressed as:

Mi=mean/middle MW of
size range i
xi = fraction of total
number of chain within the
corresponding size range

2) The weight-average MW
weight fraction of molecules
within various size ranges.
Calculated as:

Mi=mean MW within size range

i
wi =weight fraction of
molecules within the same size
interval
A typical=molecular
degree ofweight
distribution
MW with
distributionofalong
these molecular weight
averages

3)Degree of polymerization
DP Average chain size of polymer
DP average number of repeat units
(mers) in a chain
Can be expressed as :

Mn & m = number average MW &

repeat unit (mer) MW

Example

Figures of MW
distribution are
for PVC.
Calculate a)
number-average
MW b) weightaverage MW &
c) degree of
polymerisation

a) Table for number-average MW 21,150

g/mol

 b) Table for weight-average MW

23,200 g/mol

c) PVC 2 C, 3 H & 1 Cl

Molecular Structure
Linear, branced,
crosslinked, network
LINIER POLYMERS
repeat units are joined
end to end in single chains
each circle represents a
repeat unit
Melt on heating
Mechanical strength
increases with entangle
chain

Example of
Linier Polymer
Polyethylene
HDPE
PVC
Polystyrene
Nylon
fluorocarbon

BRANCHED POLYMERS
The branch considered to be part of the main
chain molecules
side-branch chains are connected to the main one
May result from side reactions that occur during
the synthesis
The chain packing efficiency reduces with
formation of side branches lowering polymer
density
By changing T, the branched polymer can be
hardened or softened
Those polymers that form linear structures may
also be branched.
E.g. HDPE (primarily a linear Polymer), while LDPE
contains short chain branches.

CROSSLINKED POLYMERS
Adjacent linear chains are joined one to another at
various positions by covalent bonds
increase strength, reduce plasticity
Achieved during synthesis or by nonreversible
chemical reaction
Often, accomplish by additive atom/molecules that
are covalently bonded to the chains
The movement of adjacent chains is greatly
restricted, afected the mechanical properties to a
great extent
E.g. rubber elastic material

NETWORKING POLYMER
Multifunctional monomers forming three or more
a polymer that is highly crosslinked may also be
classified as a network polymer.
These materials have distinctive mechanical and
thermal properties;
the epoxies, polyurethanes, and phenolformaldehyde belong to this group.
Polymers are not usually of only one distinctive
structural type. For example, a predominantly linear
polymer might have limited branching and
crosslinking.

Thermoplastic Polymers
Soften when heated (eventually liquefy), harden
when cooled reversible & may be repeated
Plastic & flexible properties
Formed at high T, cooled, remelted & reformed
into diferent shape without changing properties
Overheat material decomposes, irreversible
degradation
Most linear, some branches polymer
Fabricated by simultaneous heat & pressure
Example: polyethylene, polystyrene, PVC,
poly(ethylene terephthalate)

Thermosetting
Network polymers
Strong bonds, often formed by
condensation
Permanently hard during formation when
heat applied
Do not softened/reshaped upon
subsequent heating loss of part of the
molecule
Further heat burn/decompose
Generally harder, stronger & better
stability than thermoplastic
Most crosslinked, in that 10 to 50% of the
chain repeat units are crosslinked.
Only heating to excessive temperatures
causes severance of these crosslink
bonds and polymer degradation.

Copolymers
Polymers with more than 1 repeat unit
Diferent type depends on method synthesis &
repeat unit type
Sequencing arrangement: random, alternating,
block & graft copolymer
1) Random copolymer random distribution of
various mers
E.g nitrile rubber

 2) Alternating copolymer 4) Grafted copolymer

2 mer units alternate
homopolymer side
chain position
branches of one type may
be grafted to
homopolymer main chain
that are composed of
different mer
3) Block copolymer
identical repeat units
are clustered in blocks
along the chain

Synthetic & processing

Of polymers

SYNTHESIS
stages in polymer synthesis:
1)polymerisation, 2)additive materials, & 3)
finishing pieces

POLYMERISATION
monomers are linked together to generate
long chains composed of repeat units
raw material: derived from coal, natural
gas, petroleum
2 classifications according reaction
mechanism: addition & condensation
polymer

1) Addition polymerization
Chain reaction polymerization through free radical
polymerisation
Free radical/ unpaired electron highly reactive,
tend to rip electron from other
Free radicala are created by the division of initiator
into two fragment
Stability of free radical varies depending on the
properties of molecule
monomer units are attached one by one to an
active site to form a linear macromolecules
-Result in exact multiple of original monomer
synthesis of polyethylene, polypropylene, PVC
3 stages: initiation, propagation & termination
afect MW
Stages are controlled to ensure degree of
polymerization of product

)
)

Begins when an initiator decomposes into free radical in

the present of monomer.
The instability of C-C double bond in monomer makes
them susceptible to reaction with the unpaired electron
in the radical
active centre(location of unpaired electron) is formed
by reaction between an initiator (catalyst) species &
monomer unit

Ractive initiator; unpaired electron

* In free radical polymerisation the radical attacks one
monomer, and the electron migrates to another part.
This newly radical attack another monomer & the
process repeat.
ii) Propagation
linear growth of polymer chain by sequential addition of
monomer unit to the active growing chain molecule

1000 repeat units in 10-2 -10-3 s

In theory, the propagation continue until the supply
of monomers exhausted
However, most often the growth of the chain is
stopped by the termination reaction

iii) Termination ,there are 2 ways:

a) combination
active end of free electron from 2 growing propagation
chain may link together form 1 molecule

b) disproportionation
free radical strips a hydrogen atom from an active
chain
A C-C double bond takes the place of the missing
hydrogen

2) Condensation
polimerization

Stepwise intermolecular chemical reaction that

may involve more than 1 monomer species
By product: small MW (water) that is eliminated
(condensed)
t condensation > t addition polymerisation
Thermosetting polyester & phenol-formaldehyde,
nylons, polycarbonates
No reactant species has chemical formula in the
repeat unit; intermolecular reaction occurs
everytime a repeat unit is formed

POLYMER ADDITIVES
Additives substances introduce to
enhance/modify properties, thus more
serviceable: plasticizers, stabilizers, colorants,
flame retardants, fillers

FILLERS
# to improve tensile & compressive strength,
abrasive resistance, toughness, dimensional,
thermal stability etc
# inexpensive materials that replace some vol of
more expensive polymer reduce cost
# wood flour (sawdust), silica flour, sand, glass, clay

PLASTISIZER
- Improve flexibility, toughness; reduce hardness &
stifness
- Plasticizers are usually selected to be nonvolatile
materials and have good compatibility with the
desired polymer.
- Small plasticizer molecules occupy positions
between large polymer chain, increase interchain
distance with reduction intermolecular bonding
- Used in brittle materials (Tr): PVC
- Lower Tg at Tr, polymer may be used with
some pliability & ductility
- (Liquids having low vapor P & low MW)
phtalate ester, adipate

STABILIZERS
- Additive to counteract deterioration in some
polymers under normal environment
expose to light-UV & oxidation
# Oxidation
chemical interaction between oxygen with
polymer;
Stabilizer consume oxygen before it reaches
polymer &/ prevent the oxidation reaction
that would further damage
# Prevent photochemical degradation C
black

UV radiation
interact with & cause severe in covalent bond &
molecular chain
- Approaches to UV stabilization: add UV absorbent
& add material react with broken bond
1) Add UV absorbent material
- layer at surface as sunscreen
- to block out the radiation before penetrating
into & damage the polymer
2) Add materials that react with bond broken by
radiation before they participate in other
reactions lead more damage
#

Colorants
- give color to polymer
- added as dyes
- molecules dyes dissolve
in polymer
-added as pigment filler
materials that do
- not dissolve, remain
separate phase
- small size & refractive
index near the parent
polymers

Flame retardants
- Most all pure polymer
are flammable
- used in textile & toys
- interfere the
combustion process by
initiating diferent
combustion reaction
generate less heat,
reduce T slowing
burning

Polymer processing
There are a number of methods for
producing polymer shapes, including
molding, extrusion, and manufacture of
films and fibers.
The techniques depend to a large extent on
the nature of the polymer
The greatest variety of techniques are used
to form the thermoplastics.
The polymer is heated to near or above the
melting temperature so that it becomes
rubbery or liquid.then formed in a mold or
die to produce the required shape.

BLOW MOLDING
A hollow preform of a thermoplastic called a
parison is introduced into a die by gas
pressure and expanded against the walls of
the die.
This process is used to produce plastic
bottles, containers, automotive fuel tanks,
and other hollow shapes.

EXTRUSION
This is the most widely used technique for processing
thermoplastics.
Extrusion can serve two purposes: 1) it provides a way to
form certain simple shapes continuously, and 2)
extrusion provides an excellent mixer for additives (e.g.,
carbon black, fillers, etc.)
A screw mechanism consisting of one or a pair of screws
(twin screw) forces heated thermoplastic (either solid or
liquid) and additives through a die opening to produce
solid shapes, films, sheets, tubes, pipes, and even plastic
bags.
The extruder consist of dierent heating or cooling
zones. Extrusion can be used to make film, coat wires
and cables with either thermoplastics or elastomers.

INJECTION MOLD
Thermoplastics heated above the melting
temperature using an extruder are forced into a
closed die to produce a molding.
This process is similar to die casting of molten
metals.
A plunger or a special screw mechanism applies
pressure to force the hot polymer into the die.
A wide variety of products, ranging from cups,
combs, and gears to garbage cans, can be
produced in this manner.

THERMOFORMING
Thermoplastic polymer sheets heated to the
plastic region can be formed over a die to
produce such diverse products as egg cartons
and decorative panels.
The forming can be done using matching dies, a
vacuum, or air pressure.

CALENDARING
molten plastic is poured into a set of rolls with a
small opening.
The rolls, which may be embossed with a pattern,
squeeze out a thin sheet of the polymeroften,
polyvinyl chloride. Typical products include vinyl
floor tile and shower curtains.

SPINNING
Filaments, fibers, and yarns may be produced by
spinning.
The molten thermoplastic polymer is forced
through a die containing many tiny holes.
The die, called a spinnerette, can rotate and
produce a yarn.
For some materials, including nylon, the fiber
may subsequently be stretched to align the
chains parallel to the axis of the fiber; this
process increases the strength of the fibers.

CASTING
Many polymers can be cast into molds and
permitted to solidify.
The molds may be plate glass for producing
individual thick plastic sheets or moving stainless
steel belts for continuous casting of thinner
sheets.
Rotational molding is a special casting process in
which molten polymer is poured into a mold
rotating about two axes.

COMPRESSION MOLDING
placing the solid material before cross-linking into
a heated die
Application of high pressure and temperature
causes the polymer to melt, fill the die, and
immediately begin to harden
Small electrical housings as well as fenders,
hoods, and side panels for automobiles can be
produced by this process

TRANSFER MOLDING
A double chamber is used in the transfer molding
of thermosetting polymers.
The polymer is heated under pressure in one
chamber.
After melting, the polymer is injected into the
adjoining die cavity.
This process permits some of the advantages of
injection molding to be used for thermosetting
polymers

Polymer application
Classification is based on end-use: plastics,
elastomers, fibers, coating, adhesive, foams &
films.
Particular polymers may be used in more than 1
applications.

1) PLASTICS
materials that have structural rigidity under load
& use for general purpose application
Polyethylene, polypropylene, PVC, polystyrene,
epoxies
Some are very rigid, other are flexible exhibit
elastic & plastic deformation when stress,
sometimes experiencing deformation before
fracture

2) Elastomers
To increase tensile strength, abrasion, tear
resistance & stifness additives (C black)
Synthetic elastomers SBR (styrene butadiene
copolymers), reinforced with C back tyres
Crosslink structure
Silicon elastomers:
have a high degree of flexibility at low T (~90
C);
stable at T as high as 250 C
Resistant to weathering & lubricant oil (used in
automobile engine compartments)
Biocompatible (blood tubing)

 ELASTOMERS (rubber)

3) Fibers
long filament (L/D)=100:1
Mostly used in textile industry; woven or knit
Subjected to stretching, twisting, shearing &
abrasion
high tensile strength, high modulus elastisity &
abrasion resistance
high MW to be a strong material; will not break
during drawing
linear structure with regular order
convenience in washing thermal properties
stable in various environments: acids, base,
bleaches, dry cleaning solvent & sunlight
relative nonflammable and amenable to drying

Miscellaneous Applications
COATING
Function:
1) Protect from
corrosive/deteriorative reaction
2) Improve appearance
3) Provide electrical insulation
) Organic coaating:paint, varnish,
enamel
) Many coating are latex (stable
suspension of small insoluble
polymer particle disperse in
water); less organic solvent,
less VOC emission smog

ADHESIVES

substances used to bond 2

surfaces of solid material
(adherends)
2 types of bond: mechanical
Adhesive advantage over
& chemical
other joining
*Mechanical actual
technologies:
penetration of adhhesive
1. join dissimilar
into surface pores & crevices
materials & thin
*Chemical intermolecular
components
forces between adhesive &
2. lighter weight
adherend
3. better fatigue
Natural: casein, starch
resistance
Synthetic: polyurethanes,
4. lower manufacturing
polysiloxanes, epoxies
cost
acrylic
DrawbacksT limitation;
maintain mechanical
Factors to choose adhesive:
integrity only at low T,
1. Materials & porosities to be
strength decreases with
bond
increase in T

FILMS
Thin layer, 0.025-0.125 mm thickness
Packaging, tape
Characteristic: low density, high flexibility,
high tensile & tear strength, resistance to
moisture & chemical, low -permeability to
some gases (water vapor)
polytethylene, polypropylene, cellulose
acetate
FOAMS
plastic material with high vol of small pores
& trapped gas bubble
Thermoplastic & thermosetting:
polyurethane, rubber, polystyrene
Cushion, thermal insulation
Bubbles are generated by dissolving an
inert into molten polymer (high P); when P
reduce rapidly, the gas comes out of
solution & forms bubbles & pores that
remain in the solid as it cools