Dr.

Munir Ashraf
1
An Advanced material can be said to be a material
which has engineered properties created through the
development of specialized process and synthesis
technology.
Advanced materials outperform conventional
materials with superior properties such as toughness,
hardness, durability and elasticity.
They can have novel properties including the ability to
memorize shape or sense changes in the environment
and respond.

Introduction
2
Advanced Materials
Polymeric
materials
Ceramics Metals Composites
Introduction
3
Polymeric
materials
Non-functional
polymers
Functional
polymers
Introduction
Fibrous Non fibrous
Polyamide HP P.E
Carbon
Fibers
Chemically
inert fibers
Adaptive conductive Piezoelectric
4
A polymer is constructed by connecting the repeat units together
successively along the main chain.
The repeat units are made of monomeric units
The monomeric units are made of monomers

Polymeric Materials General Introduction
Types of polymerization
Addition polymerization:
The monomer molecules simply add on to each other to form a long-
chain polymer

Condensation Polymerization:
Molecules of monomer polymerise and, at the same time, a small
molecule (such as water, ammonia, carbon dioxide) is given off.
Condensation polymerisation usually involves two different monomers
5
Repeat units of common polymers
Polymeric Materials General Introduction
6
The size of polymer chain can be characterized by measuring the
polymer chain
The size of polymer chain increases with increase in molecular weight
The molecular weight of polymer is measured by degree of
polymerization N , i.e. the number of repeating units in the polymer
chain.
M = NM0
But in real polymers, all polymer chains are not of same size.

Therefore, average weight of polymer is calculated


Polymeric Materials General Introduction
7
Number-average molecular weight (
n
)
Based on methods of counting the number of molecules in a given weight of polymer
The total weight of a polymer sample, w, is the sum of the weights of each
molecular species present


Polymeric Materials General Introduction

1 1 i
i i
i
i
M N w w

1
1
1 i
i
i
i i
i
i
n
N
N M
N
w
M
N = number of molecules
M = molecular weight
8
Polymeric Materials General Introduction
Weight-average molecular weight (
w
)
The weight average molecular weight depends not only on the number of molecules
present, but also on the weight of each molecule. To calculate this, N
i
is replaced
with N
i
M
i
.


w = weight fraction
M = molecular weight
N = number of molecules

Polydispersity Index
9
Effect of Molecular Weight
The properties of polymers depend on molecular weight
To have physical properties, the molecular weight of polymer must
exceed Critical Molecular Weight.
Polymeric Materials General Introduction
10
Bonding in Polymers
The polymers contain two types of bonds

Primary bonds
Covalent bonds

Secondary bonds
Hydrogen bonds
Dipole interaction
Van de Waals forces
Ionic

Polymeric Materials General Introduction
The primary bonds hold atoms together in a
polymer chains

The Secondary bonds hold polymer chains
together
11
Tacticity
Tacticity is a term used to describe the way pendent groups on a polymer chain
are arranged on a polymer backbone.










Tacticity determines the packing of polymer chains and ultimately properties
of polymers.
Isotactic and syndiotactic polymers chains pack together tightly.
Polymeric Materials General Introduction
12
Morphology of Polymers
The geometric arrangement of molecuar chains exerts significant
effect on polymer properties.
According to chain arrangements, the polymers can be amorphous,
crystalline or semi-crystalline.
Polymeric Materials General Introduction
Amorphous
13
Transitions in Polymers
Glass transitions
Melting pont
Polymeric Materials General Introduction
14
Mechanical Properties of Polymers
Strength
The stress needed to break
Elongation
Elastic elongation
Plastic elongation



Yield Point
It is a measure of the strength of the material and of its resistance to
permanent deformation


Polymeric Materials General Introduction
15
Modulus
The resistance to deformation is called modulus
Toughness
Toughness is a measure of the energy a sample can absorb before
it breaks
Polymeric Materials General Introduction
16
Fibrous Polymers
17
The polymers of which fibers are prepared.
These normally semi-crystalline materials

Fibrous Polymers
Fibers
Conventional Fibers
High Perfomance Fibers
Special technical functions that require
specific performance properties unique to
these fibers.
General purpose fibers designed cater the
day to day requirements
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The high perfomance fibers are characterized by
Tensile strength and modulus
Resistance to heat and flame
Resistance to chemical agents that normally degrade
conventional fibers.
The high performance fibers include
aramids
High performance polyethylene
Carbon fibers
Glass fibers
Ceramic fibers
Chemically resistant fibers
Thermally resistant fibers

Fibrous Polymers
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Adaptive polymers
Shape memory materials
Adaptive gels
Phase change materials
Shape memory composites
Adaptive polymeric nanofibers
Conducting polymeric materials
Piezoelectric polymers



Fibrous Polymers
20
The term aramid is short for aromatic polyamide.
manufactured fiber in which the fiber-forming substance is a long-
chain synthetic polyamide in which at least 85% of the amide (-CO-
NH-) linkages are attached directly between two aromatic rings.
These fibers have much superior mechanical properties than steel and
glass fibers on an equal weight basis, and maintain these properties at
high temperatures.
They are good replacement for metal wires and inorganic fibers in
some high performance applications
By definition, the aramid family will cover Kevlar, Nomex, Technora,
Teijinconex, Twaron etc fibers.
aramid Fibers
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Like nylons these can also be classified as AB and
AABB type polymers.
aramid Fibers
Poly (p-benzamide)
Twaron
Poly (m-phenylene isophthalamide) MPDI
Nomex
Poly(p-phenylene terephthalamide) PPTA or PPD-T

Kevlar
Copolymer (Technora)
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Structural difference between polyamides and aramids
aramid Fibers
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Preparation of fibers
Polymerization
Extrusion into filaments
Preparation of staple fibers
Polymerization
These are generally prepared by low temperature solution
polycondensation of various aromatic amines and diacids or diacid
chlorides.
The usual melt polycondensation methods for the preparation of
aliphatic polyamides are not suitable
The preferred solvents are dimethyl acetamide (DMAc), N-methyl-2-
pyrrolidone (NMP), hexamethyl phosphoric triamide (HMPA), tetramethyl
urea (TMU).
aramid Fibers
Terephthaloyl chloride (TCl)
p-phenylene diamine (PPD)
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Preparation of fibers
aramid Fibers
Polymerization
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Fiber Extrusion
Dope Structure
The linear aramid molecular structures, such as PBA and PPD-T are Nematic
liquid crystals
The liquid crystal state is a distinct phase between the crystalline (solid) and
isotropic (liquid) states
Molecular bundles (mesogens) point along a common axis, called the director

aramid Fibers
26
Fiber Extrusion
The aramids decompose before they melt, therefore, they are produced by dry jet wet
spinning methods and wet spinning

Wet spinning





The spinneret is immersed in coagulation bath
The extruded fibers coagulate immediately without alignement of
domains
The ;echniacal properties are not that good



aramid Fibers
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Fiber Extrusion
Dry jet-wet spinning
Improved properties are achieved using dry-jet-wet spinning technique

aramid Fibers
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Fiber Extrusion
The polymer dope (in concentrated sulphuric acid) is extruded through spinnerets at
about 90 C through about 1 cm air gap into coagulation bath
The fiber precipitates in the air gap and the acid is removed in the coagulation bath
The spinneret capillary and air gap cause rotation and alignment of domains
resulting in highly crystalline and oriented as-spun fibers

aramid Fibers
When the polymer solutions passes through the
capillary hole, the capillary shear causes some of
the liquid crystal domains to orient along the
direction of shear
The fiber is highly oriented and does not
require a subsequent drawing process, as is
required for conventional fibers.
The attenuated filament, after washing,
neutralization and drying results in highly
crystalline, high strength, high modulus
fiber
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Fiber Extrusion
Schematic of Crystalline Orientation of para-aramid fiber:
(a) random; (b) radial; (c) tangential.






Using dry-jet wet spinning radial crystalline
orientation is obtained.



aramid Fibers
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fiber Heat Treatment
The physical and tensile properties of as-spun aramid fibers can be further improved by
heat treatment under tension
aramid Fibers
In wet spun yarns, both tenacity and modulus
increase exponentially with increasing
temperature (and draw ratio)
The heat treatments promote molecular
chain displacement, thus allowing the
formation of regular chain bonding
between highly oriented regions of
crystalline order
The wet spun yarns show major increase in
crystallinity, structure perfection, and
orientation
In dry jet spun yarns, a jump in modulus is
observed but the tenacity remains constant
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Structure of aramid fibers
Aramids particularly Kevlar can acquire a high degree of alignment of
long straight polymer chains parallel to fiber axis due to the liquid
crystalline domains orientation and alignment in flow direction
Kevlar fiber contains several levels of superimposed microscopic and
macroscopic structures including the crystal lattice, pleated structure,
fibrillar structure and skin-core structure.
aramid Fibers
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Structure of aramid fibers
The sheets are held together in Kevlar fibers by the 'random' but
'continuous' intermolecular forces between adjacent layers of molecules.











The molecules form a planar array with interchain hydrogen bonding
The stacking sheets form a crystalline array, but between the sheets the
bonding is weak

aramid Fibers
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Properties of aramid fibers
The aromatic ring, as well as the conjugation of electrons gives the
material high thermal stability, chemical stability and mechanical
stiffness.
The hydrogen bonds in the transverse direction and covalent bonds in
the fiber axis direction lead to a great mechanical property anisotropy.
aramid Fibers
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Properties of aramid fibers
The functional properties of aramid fibers, particularly tensile properties are related to
the fiber structure at molecular level
The polymer chain rigidity, crystalline orientation and crystallinity are the key properties
governing the final fiber properties.
aramid Fibers
35
Properties of aramid fibers
Aramid fibers are characterized by medium-to-ultrahigh strength, medium-to-
low elongation and moderately high-to-ultra high modulus with the densities
for crystalline fibers ranging from 1.35 to 1.45 g/cm
3
fibers of low orientation MPD-I (eg Nomex) have a density of 1.35 g/cm
3
. fibers
from PPD-T (eg Kevlar) have a density of ~ 1.45 g/cm
3
Heat and flame-resistant aramid fibers contain a high proportion of meta-
oriented phenylene rings, whereas ultra high strength high modulus fibers
contain mainly para-oriented phenylene rings
aramid Fibers
36
Chemical Properties
Moisture absorption
The hydrophilicity of amide linkage leads to moisture absorption by all aramids
In addition to chemical composition, fiber structure also plays a critical role in
determining the moisture absorption
Chemical resistance
Very good chemical resistance to the attack of organic solvents and aqueous salt
solutions
Strong acids and bases do attack the fiber at elevated temperatures, causing
hydrolysis of amide linkage and loss of strength.
These fibres are more resistant to acids than nylon 6,6 fibres, but not as resistant as
polyester fibres
Dyeability
Aramid fibres are exceedingly difficult to dye by conventional methods due to their
very high Tg
UV stsbility
The aromatic nature of p-aramid is responsible for a substantial absorption of UV
light, which in turn leads to a change of colour due to oxidative reactions as well as
drop in fibre properties.

aramid Fibers
37
Thermal Properties
Aramid fibres do not melt in the conventional sense because decomposition occurs
simultaneously
Some aramid fibres such as Nomex, shrink away from a high heat source or from a
flame.
Aramid fibres characteristically burn only with difficulty because of high LOI values.
Burning produces a thick char that acts as a thermal barrier.
The bond dissociation energies of C-C and C-N bonds in the main chain are
significantly higher in aromatic compounds than those in aliphatic ones, which gives
higher thermal stability to aromatic materials.
Excellent thermostability of poly(p-phenylene benzobisthiazole) is due to its fully
aromatic character and highly rigid molecule.
Introduction of flexible groups such as -O- into main chain (as in Technora) leads to
a more flexible chains and lower thermal stability
The conjugation between the amide groups and the aromatic ring in p-aramids is
responsible for the yellow color and increased chain rigidity which help into excellent
retention of physical properties at elevated temperature.
aramid Fibers
38
Mechanical Properties
Typical stress-strain curve of Kevlar aramid yarn as compared to other industrial
filament yarns
aramid Fibers
The outstanding high strength of Kevlar can be
attributed to:

Its aromatic nature and amide group.

High crystallinity and orientation.

Individual polymer strands of Kevlar are held
together by H-bonds that form between the polar
amide groups on adjacent chain.

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Bending strength
aramid Fibers
40
Comparison of Aramid with other fibers
aramid Fibers
41
Compressive strength
When subjected to axial compression, the fibre exhibits a yield point at a
compressive strain of 0.3-0.5%.
This corresponds to formation of structural defects known as Kink bands (at 45-60
to the fibre axis)
aramid Fibers
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Compressive strength
The compressive buckling of the aramid molecules is by molecular
rotation of the amide C-N bond

aramid Fibers
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Fatigue
Aramid like Kevlar have excellent Fatigue behavior
With tension fatigue no failure is observed even at loads
as high as 60% of breaking strength and 10
7
cycles.

Creep
These fibre exhibit very low creep even at elevated temperature.
At a load of 0.5 of breaking load after 10
5
sec, creep strain for Kevlar is only
0.3%.

aramid Fibers
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Application
Presentation
aramid Fibers
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