You are on page 1of 89

Polymers

What is polymer
A polymer is a material whose
molecules contain a very large
number of atoms linked by
covalent bonds, which makes
polymers macromolecules.
Polymers consist mainly of identical
or similar units joined together.
The unit forming the repetitive
pattern is called a "mer" or
"monomer".
Usually the biggest differences in
polymer properties result from how
the atoms and chains are linked
together in space.
Polymers that have a 1-D structure
will have different properties than
those that have either a 2-D or 3-D
structure.

Polymers are long chain


molecules

What is polymer
Polymers are a very important class of materials.
Polymers occur naturally in the form of proteins,
cellulose(plants), starch(food) and natural rubber.
Engineering polymers, however, are usually synthetic
polymers.
The field of synthetic polymers or plastics is currently one of
the fastest growing materials industries.
The interest in engineering polymers is driven by their
manufacturability, recyclability, mechanical properties, and
lower cost as compared to many alloys and ceramics.

Degree of Polymerization
Number of monomer units in the chain
N >> 1.
For synthetic macromolecules usually
N=102-104
For natural macromolecules like DNA
N=109-1010
Number of monomers in a chain is
called degree of polymerization (DP).

Average degree of polymerization


The degree of polymerization (DP) in a polymer molecule is the
number, n, of repeating units in the polymer chain.

The molecular weight of a particular polymer molecule is a product


of the degree of polymerization and the molecular weight of the
repeating unit.
For instance a particular polyethylene molecule with DP = 1000 will
have a molecular weight of 28,000.
Because polymeric materials do not consist of strictly identical
molecules, but instead are a mixture of many species having
different values of DP, the DP of the material only is an average DP
value.
Hence, measured polymer molecular weights are only average
values.

What governs physical


properties of polymers
Monomer units are connected in the chain.
They do not have the freedom of independent motion
low number of degrees of freedom
(unlike systems of disconnected particles, e.g. low molecular
gases and liquids).
Polymer systems are poor in entropy.
Polymer chains are generally flexible.

Polymer molecular structure


1.
2.
3.
4.

Chemistry (Mer composition)


Size (Molecular Weight)
Shape (Chain twisting, entanglement)
Structure- Linear (Isomers-Stereo and Geometrical)
Branched
Cross-linked
Ring
Network

Types of Polymer Molecules (Structure)


1. Homopolymers: all monomer units are the

same.
2. Copolymers : monomer units of different
types.
(for example, proteins - 20 types of units
DNA - 4 types of units ).
Sequence of monomer units along the chain is
called primary structure.
3. Bifunctional (2-D), Chain structure, ethylene
4. Trifunctional (3-D) Network structure, Bakelite

Different kind of copolymers


The polymerization of a mixture of two monomers
of suitable reactivity leads to the formation of a
copolymer.
Random copolymer: A polymer in which two types
of mer units have entered the chain in a more or less
random fashion.
Alternating Copolymer: both mer units occur
alternately in the structure
If chains of one homopolymer are chemically joined
to chains of another, the product is called a block
copolymer or a graft copolymer.

Different kind of copolymer


A-B-A-A-B-B-B
(Random copolymer)
A-B-A-B-A-B-A-B
(Alternating copolymer)
A-A-A-A-A-B-B-B-B(block copolymer)
A-A-A-A-A
|
B
|
B
|
B
(Graft polymer)

Branched macromolecule

Ring macromolecules

Polymers are special

Physical states of Polymer


1.Partially crystalline state
2. Viscoelastic state (polymer melt)
3. Highly elastic state ( e.g. rubbers)
4. Glassy state ( e.g. organic glasses from poly(styrene),
poly(methylmethacrylate), poly(vinyl chloride)).
 Polymers are large molecules with strong intermolecular forces and

tangled chains, and do not have a vapor phase - they decompose before
the temperature gets high enough to form a vapor.
 The length of polymer molecules also makes it difficult for the large
crystals found in the solid phases of most small molecules to form.
 Instead solid polymers can be modeled in terms of two phases - crystalline and
amorphous.
 Thus the behavior of polymers can better be understood in term of the three
phases: melt, crystalline, and amorphous.

Crystaline polymer
Crystalline Polymer
Highly crystalline polymers are rigid, have high melting point, and
less affected by solvent penetration.
Crystallinity makes a polymers strong, but also lowers their impact
resistance.
As an example, samples of polyethylene prepared under high pressure
(5000 atm) have high crystallinities (95 - 99%) but are extremely
brittle.

Amorphous Polymers
Polymer chains with branches or irregular pendant groups cannot pack
together regularly enough to form crystals.
These polymers are said to be amorphous.

Molecular weight of Polymer


Polymers are different. Imagine polyethylene. If we have a sample of
polyethylene, and some of the chains have fifty thousand carbon atoms in
them, and others have fifty thousand and two carbon atoms in them, this
little difference isn't going to amount to anything.
To know the truth, one almost never finds a sample of a synthetic
polymer in which all the chains have the same molecular weight.
Instead, we usually have a bell curve, a distribution of molecular
weights. Some of the polymer chains will be much larger than all the
others, at the high end of the curve. Some will be much smaller, and at
the low end of the curve. The largest number will usually be clumped
around a central point, the highest point on the curve.
So we have to talk about average molecular weights when we talk about
polymers. The average can be calculated in different ways, and each
way has its own value.

Different average molecular weights


The Number Average Molecular Weight, Mn
The number average molecular weight is not too difficult to understand. It
is just the total weight of all the polymer molecules in a sample, divided
by the total number of polymer molecules in a sample.
The Weight Average Molecular Weight, Mw
The weight average is a little more complicated. It's based on the fact that
a bigger molecule contains more of the total mass of the polymer sample
than the smaller molecules do.
The Viscosity Average Molecular Weight, Mv
Molecular weight can also be calculated from the viscosity of a polymer
solution. The principle is a simple one: Bigger polymers molecules make
a solution more viscous than small ones do.
Of course, the molecular weight obtained by measuring the viscosity is a
different from either the number average or the weight average molecular
weight. But it's closer to the weight average than the number average.

Number averaged molecular weight


Suppose a mixture of polymer molecules with different molecular weights in
which the number of molecules having a particular molecular weight, Mi,
is given by Ni. The "number-average" probability of a given mass being
present is

and the number-average molecular weight is given by the formula

The number average is the simple arithmetic mean, representing the total
weight of the molecules present divided by the total number of molecules.
Most thermodynamic measurements are based on the number of molecules
present and hence depend on the number-average molecular weight:
examples are the colligative properties, osmotic pressure and freezing
point depression.

Weight average molecular weight


The probability factor in a weight-average emphasizes the mass
of the molecules so that the heavier molecules are more
important.
The weight-average molecular weight formula is

 Molecular weight measurements that depend on the contributions


of molecules according to their sizes give weight-average
molecular weights.
 Light scattering and ultracentrifuge methods are examples of
this type of technique.

Measure of Polydiversity
The weight-average molecular weight is larger than or equal to the
number-average molecular weight.
 The ratio of the weight-average and number-average molecular
weights, is a measure of the polydispersity of a polymer mixture .
 Signifies how widely distributed the range of molecular weights are
in the mixture.
 A ratio that is around 1.0 indicates that the range of molecular
weights in the mixture is narrow
 A high ratio indicates that the range is wide. With rare exceptions,
all synthetic polymers are polydisperse.

Threshold Molecular Weight


Polymer chemists sometimes refer to the threshold
molecular weight below which an oligomer will not display
the properties needed for a particular application.
The value of the threshold molecular weight depends on
the application.

If the polymer is to be used as an adhesive, the required


molecular weight may be relatively low.

If the polymer is to be used in a trash barrel on the other


hand, a high molecular weight is required.

Commercial Polymer Range

Beyond
the
critical
degree
of
polymerization, as molecular weight
grows larger polymer strength increases
rapidly. Eventually, as is shown in the
diagram at the right, the strength levels
off.
The threshold molecular weight is a lower
limit for the molecular weight required
for a given commercial application
As the molecular weight increases the
chains also entangle more, which
increases the viscosity of the polymer
melt.
In most industrial applications a polymer
is melted as it is processed so that it will
flow into a mold or through an orifice.
Eventually the viscosity gets so high that
the polymer cannot be processed easily,
establishing an upper molecular weight
limit beyond which it is prohibitively
expensive to process the polymer.

Commercial Polymer Range


For a particular application
only a certain molecular weight
range is practical for a given
polymer.
This range is a compromise
between optimum properties
and ease of processing.
Most of the practically useful
polymers have a DP between
200 to 2000, corresponding to a
molecular weight range from
20,000 to 200,000.

Polymer structures: one


dimensional polymers
One dimensional polymers are most common.
They can occur whenever 2 reacting chains join to
make a chain.
If the long-chains pack regularly, side-by-side, they
tend to form crystalline polymers.
If the long chain molecules are irregularly tangled, the
polymer is amorphous since there is no long range
order.
Sometimes this type of polymer is called glassy.

Polymer structures: Two


dimensional polymers
Two dimensional polymers are rare, the best
example of one would be graphite.
It is the structure of graphite which provides its
great lubricating capability.
The condition to form this planar structure is to
have 3 or more active groups all directed in the
same plane and capable of forming a planar
network.
This structure offers low shear strength and good
lubricating properties.

Polymer structures: Three


dimensional polymers
Crystalline Diamond is an example of the 3dimensional crystalline polymer in which carbon is
linked to four corners of the tetrahedra and these
are packed with long range order in space to form a
lattice.
Diamond has properties which are much more like
ceramics than polymers in terms of mechanical
behavior (high melting point, modulus, hardness,
strength, and fracture behavior)

Classification of polymers-Thermal response


Thermoplastic Polymers
These are linear, one-dimensional polymers which have
strong intramolecular covalent bonds and weak
intermolecular van Der Waals bonds.
At elevated temperature, it is easy to "melt" these bonds
and have molecular chains readily slide past one another.
These polymers are capable of flow at elevated
temperatures, can be remolded into different forms, and in
general, are dissolvable.
A thermoplastic, under the application of appropriate
heat, can be melted into a "liquid" state.

Thermosetting Polymers
These are three-dimensional amorphous polymers which are
highly crosslinked (strong, covalent intermolecular bonds)
networks with no long-range order.
Thermosetting polymers are those resins which are "set" or
"polymerized" through a chemical reaction resulting in
crosslinking of the structure into one large 3-dimensional
molecular network.
Once the chemical reaction or polymerization is complete, the
polymer becomes a hard, infusible, insoluble material which
cannot be softened, melted or molded non-destructively.
A good example of a thermosetting plastic is a two-part epoxy
systems in which a resin and hardener (both in a viscous state)
are mixed and within several minutes, the polymerization is
complete resulting in a hard epoxy plastic.

Rubbers and Elastomers


In general, a rubber material is one which can be stretched
to at least twice its original length and rapidly contract to its
original length.
Rubber must be a high polymer (polymers with very long
chains) as rubber elasticity, from a molecular standpoint, is
due to the coiling and uncoiling of very long chains.
To have "rubber-elastic properties" a rubber materials' use
temperature must be above its glass transition
temperature and it must be amorphous in its unstretched
state since crystallinity hinders coiling and uncoiling.
Rubbers are lightly crosslinked in order to prevent chains
from slipping past one another under stress without
complete recovery

Classification of polymers: Fibers


Many polymers used for synthetic fibers are identical to those
used in plastics but the two industries developed separately
Synthetic fibers include Kevlar, carbon, PE, PTFE, and nylon while natural
fibers include silk, cotton, wool and wood pulp.

A fiber -

aspect ratio (length/diameter) of at least 100.

Synthetic fibers are spun into continuous filaments, or chopped


in shorter staple which are then twisted into thread before
weaving.
The thickness of the fiber is expressed in terms of denier which is
the weight in grams of a 9000-m length of fiber.
Stresses and strength of fibers are reported in terms of tenacity in
units of grams/denier.

Classification of polymers:
Liquid crystal
The structure of liquid crystals is unique.
It is a near-ideal in structure with most of its molecules
virtually stretched out.
Not useful for textiles, but excellent for composite
reinforcement.
Continuous crystals are readily attained in liquid
crystalline polymers, as the molecules are already
aligned in parallel positions in the melt
The continuous morphology would require elaborate
processing to avoid chain entanglement and chain
folding.

Polymer Synthesis
There are two major classes of polymer formation mechanisms
Addition polymerization: The polymer grows by sequential
addition of monomers to a reactive site
Chain growth is linear
Maximum molecular weight is obtained early in the
reaction
Step-Growth polymerization: Monomers react together to
make small oligomers. Small oligomers make bigger ones, and
big oligomers react to give polymers.
Chain growth is exponential
Maximum molecular weight is obtained late in the reaction

Addition Polymerization
In*

A
Initiation

In

A*

Addition Polymerization
Propagation
In*

A
Initiation

In

A A*

Addition Polymerization
Propagation
In*

A
Initiation

In

A A A*

Addition Polymerization
In*

nA

In

A A A A*

Initiation

In

Propagation

A A A A A*
n

*A

*A

A A A A
m

A A A A
m

In

In

A A A A A

A A A A A

In

A*

A A A A A
n

Combination

B A A A A
m

Chain Transfer
New reactive site
is produced

Disproportionation
Termination
Reactive site is consumed

MW

MW
0

100
% conversion

A A A A A

k propagation
k ter mination

Types of Addition Polymerizations


Anionic
Ph
C3H7

Li

Li+

C4H9

Ph

Li+

C4H9

Ph

Ph

Ph

Radical

PhCO2

Ph

n
Ph

PhCO2

Ph

Cationic
Ph
Cl3Al OH2

PhCO2
Ph

Ph

n
Ph

H
Ph
HOAlCl3

HOAlCl3

Ph

Ph

Step-Growth Polymerization
n

Stage 1

Consumption
of monomer

Stage 2
Combination
of small fragments

Stage 3
Reaction of
oligomers to give
high molecular
weight polymer

Step-Growth Polymerization
Because high polymer does not form until the end
of the reaction, high molecular weight polymer is
not obtained unless high conversion of monomer is
achieved.
1000

Xn =
100

Xn = Degree of
polymerization
p = mole fraction monomer
conversion

1
1 p

10

1
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Mole Fraction Conversion (p)

0.8

0.9

Polymer synthesis: step growth


Polymerization is the process by which monomers (smaller
chemical units) are combined to form a polymer.

Step Growth Polymerization


In step growth polymerization or condensation
polymerization, chains of any length x and y combine to
form long chains:
x-mer + y-mer (x + y)-mer
The term condensation polymerization is mainly
characterized by the fact that the early reaction yields water.
More recently it has been found that several other polymer
reaction condense out products such as HCl or will condense
out no products at all.

Step growth (example)


In a step-reaction polymerization reaction, sometimes called
condensation polymerization, the polymer chains grow by
reactions that occur between two molecular species.
An example is the polymerization reaction involving
terephthalic acid and ethylene glycol, both of which are
bifunctional.
Polymer formation begins with one diacid molecule reacting
with one dialcohol molecule to eliminate a water molecule
and form an ester.
The ester unit has an alcohol on one end and acid on the
other, which are available for further reactions.

Step growth (example)

Step growth (example)


The eventual result is a polyester called poly(ethylene
terephthalate) or more commonly, PET.

PET is the plastic in soda bottles. It can be represented with a


shorthand notation.

Step growth
Step growth polymerization is used to yield
branched as well as networked polymers.
true initiator of a network structure lines in a
multifunctional monomer.
As the length and frequency of branches on the polymer
chain increases so does the probability that the branches will
reach from chain to chain.
When all the chains are connected together the entire
polymer mass becomes one giant molecule.
Consider a bowling ball, it has a molecular weight on the order
of 1027 g/mol, and it is one giant molecule. Crosslinked or
network polymers form in one of two ways:
1. Starting with tri functional (or higher) monomers
2. Chemically creating crosslinks from previous linear polymers

Chain growth/ Addition


polymerization
Chain growth polymerization involves an active chain site which
reacts with an unsaturated (or heterocyclic) monomer such that
the active site is recovered at the chain end.
Vinyl polymers were probably the first to be synthesized in this
manner when in 1839 Simon reported the conversion of styrene to
some gelatinous mass.
In general, high molecular weight species are made by the
successive addition of new monomers to the chain end.

Chain growth
There are several different techniques of synthesis
depending on the active site. These are:

Active Site

Synthesis Technique

Free Radicals

Free Radical
Polymerization

Carbanions

Anionic Polymerization

Carbenium Ions

Cationic Polymerization

Coordination Bonds
with Transition Metals

Ziegler-Natta
Polymerization

Transitions in Polymer: Glass


Transition temperature
Amorphous polymers exhibit two distinctly different types of
mechanical behavior.
Some polymers like polymethyl methacrylate and polystyrene
are hard, rigid, glassy plastics at room temperature while
others like polybutadiene and polyethyl acrylate are soft,
flexible, rubbery materials at room temperature.
There is a temperature, or range of temperatures, below
which an amorphous polymer is in a glassy state and above
which it is rubbery.
This temperature is called the glass transition temperature, Tg,
and it characterizes the amorphous phase.
It is especially useful since all polymers are amorphous to
some degree, they all have a Tg.

Molecular Motions in Amorphous Polymers


The molecular motions occurring inside an amorphous polymer
influence the glass transition temperature.
The important motions are:
1. Translation motion of entire molecules (permits flow)
2. Cooperative wriggling and jumping of segments of molecules
(permits flexing and uncoiling leading to elasticity)
3. Motions of a few atoms along the main chain or side groups on the
main chain .
4. Vibrations of atoms about equilibrium position
The glass transition temperature is the temperature at which there
is only enough energy for motions (3) and (4) to occur.
Below the glass transition temperature processes (1) and (2) are
frozen out.
This makes polymer glassy below Tg & rubbery above Tg.

Factors Influencing Glass


Transition Temperature
In general the glass transition temperature depends on five other
factors which are:
1. Free volume of the polymer vf, - Volume of the polymer mass
not actually occupied by the molecules themselves. The higher
the vf is, the more room the molecules have to move around
and the lower is Tg. For all polymers the ratio of the free volume
vs the total volume (vf/v) is about 0.025 at Tg.
2. The attractive forces between the molecules. The more strongly
the molecules are bound together , the more thermal energy must
be applied to produce motion and hence more will be Tg
3. The internal mobility of the chains, or their freedom to rotate
about the bonds.

Factors Influencing Glass


Transition Temperature
4. The stiffness of the chains- Stiff chains cannot easily coil and
fold, causing Tg to be higher for polymers with stiff chains.
Polymers with parallel bonds in the backbone, like polyimides,
and polymers with highly aromatic backbones have extremely
stiff chains and thus high Tg's.
5. The chain length. The glass transition temperature varies
according to the relation:
Tg = Tinf - C/x
where C is a polymer specific constant, Tinf is the asymptotic
value of the glass transition temperature for a chain of length
infinity and x is the length of the chain.
This relationship shows that shorter chains can move easier
than longer chains. For most commercial polymers Tg ~ Tinf,
since x is quite long.

Relation between chain length and


bond length
For a linear chain polymer, the chain length

L = N d s in

where is the angle between adjacent


backbone chain atoms, d is the bond length,
and N is the total number of bonds in the
molecule

Determination of the Glass Transition


Temperature
The most common method used to determine Tg is to observe
the variation of a thermodynamic property with T.
Tg determined in this manner will vary somewhat depending
on the rate of cooling or heating.
This reflects the fact that long entangled polymer chains
cannot respond instantaneously to changes in temperature.
At the glass transition temperature a thermodynamic property
will exhibit a discontinuity with temperature.
A second order thermodynamic transition.

Crystallinity in polymer
Crystallinity of a polymer material refers to the degree to
which polymer molecules are oriented into repeating
patterns.
For same material, density of crystalline polymer is greater
than that of amorphous polymer.
Chains are more closely packed together for the crystalline
structure.

c ( s a)
% crystallinity =
X 100
s ( c a)

Degree of crystalline character of a polymer depends on the


rate of cooling during solidification as well as on the chain
configuration.
Crystallization easy in linear polymers and branching
(networking) interferes with crystallization.
Lesser crystallinity in bulkier or larger side groups.

Mechanical properties: Elongation


Strength tells us is how much stress is needed to break something.
Elongation is a type of deformation. Deformation is simply a
change in shape that anything under stress.
Tensile stress, the sample deforms by stretching, becoming longer elongation.
Generally, % elongation- length of the polymer sample after it is
stretched (L), divided by the original length of the sample (L0), and
L
then multiplied by 100.
100 = % of elongation
L0
Ultimate elongation -amount by which sample can be stretched
before breaking.
Elastic elongation is the percent elongation you can reach without
permanently deforming your sample
Signifies how much it can be stretched, and still the sample snap
back to its original length on releasing the stress on it.
Important for an elastomer. Elastomers should be able to stretch a
long distance and still bounce back.
can stretch from 500 to 1000 % elongation and return to their
original lengths without any trouble

Modulus
Elastomers require high elastic elongation.
But, for some other types of materials, like plastics, its usually
better that they not stretch or deform so easily.
To know, how well a material resists deformation, we measure
parameter called modulus.
To measure tensile modulus, the stress exerted on the material is
measured.
The amount of stress is slowly increased and the elongation of the
sample at each stress level is measured.
This continues until the sample breaks. Then we make a plot of
stress versus elongation, like this:

Modulus
Stress-strain curve. (Strain is any kind of deformation, including
elongation. (Elongation specifically related to tensile strain.)
The height of the curve when the sample breaks is the tensile strength,
Tensile modulus is the slope of this plot.
If the slope is steep, the sample has a high tensile modulus, which
means it resists deformation.
If the slope is gentle, then the sample has a low tensile modulus, which
means it is easily deformed.
There are times when the stress-strain curve isn't nice and straight. For
some polymers, especially flexible plastics, we get odd curves that
look like this:

Modulus
The slope does not remain constant as stress increases.
The slope, that is the modulus, changes with stress.
In such cases, we usually take the initial slope as the
modulus, in the stress-strain curve given earlier.
In general, fibers have the highest tensile moduli, and
elastomers have the lowest, and plastics have tensile
moduli somewhere in between fibers and elastomers.
Modulus is measured by calculating stress and dividing
by elongation, and would be measured in units of stress
divided by units of elongation.
But since elongation is dimensionless, it has no units by
which we can divide.
So modulus is expressed in the same units as strength,
such as N/cm2.

In real polymers

Interpretation of the curves


green plot corresponding to rigid plastics such as polystyrene,
poly(methyl methacrylate or polycarbonate can withstand a good
deal of stress, but they won't withstand much elongation before
breaking.
There isn't much area under the stress-strain curve at all.
So materials like this are strong, but not very tough.
Also, the slope of the plot is very steep, which means that it takes a
lot of force to deform a rigid plastic.
So it's easy to see that rigid plastics have high moduli.
In short, a rigid plastics tend to be strong, resist deformation,
But, they tend not to be
very tough, that is,
they're brittle.

Flexible plastics like polyethylene and polypropylene are different


from rigid plastics in that they don't resist deformation as well, but
they tend not to break.
The ability to deform is what keeps them from breaking.
Initial modulus is high, that is it will resist deformation for a while,
but if enough stress is put on a flexible plastic, it will eventually
deform.
e.g. piece of a plastic bag- If stretched, it will be very hard at first, but
once you've stretched it far enough it will give way and stretch easily.
The bottom line is that flexible plastics may not be as strong as rigid
ones, but they are a lot tougher.
It is possible to alter the stress-strain behavior of a plastic with
additives called plasticizers.
A plasticizer is a small molecule that makes plastics more flexible
e.g. without plasticizers, PVC, is a rigid
plastic-used for water pipes.
But with plasticizers, PVC can be made
flexible enough to use to make things
like inflatable swimming pool toys.

Fibers like KevlarTM , carbon fiber and nylon fibre stress-strain curves
Like the rigid plastics, they are more strong than tough, and don't deform
very much under tensile stress. high strength in fibres.
They are much stronger than plastics, even the rigid ones, and some
polymeric fibers, like KevlarTM, carbon fiber and ultra-high molecular
weight polyethylene have better tensile strength than steel.
Elastomers like polyisoprene, polybutadiene and polyisobutylene have
completely different mechanical behavior from the other types of
materials.
Stress strain curve of Elastomers have very low moduli.
Very gentle slope of the elastomers,
Easy to stretch or bend a piece of rubber.
If elastomers didn't have low moduli,
they wouldn't be very good elastomers,

Factor influencing mechanical properties of polymer


temperature
strain rate,
molecular weight,
degree of crystallinity
Quantitative measure of cystallinity
Additives (substances which can change
mechanical, chemical and physical properties of
polymer to a high degree which cant normally be
accomplished by changing the molecular structure)

Electrical properties of polymer


Most of the polymers are
normally insulators specially
when they are in pure form.
This will be clear from the
following table.
But by suitable choice of
doping one can make ionically
conducting and electronically
conducting polymer.

polymer

Conductivity
in 1 m 1

Phenol
formaldehyde

10-9-10-10

Polymethyl <10-12
methacrylate
Poyethylene 10-15-10-17

What is conductivity?
Conductivity can be defined simply by Ohms Law.
V= IR
Where R is the resistance, I the current and V the voltage present in the
material. The conductivity depends on the number of charge carriers
(number of electrons) in the material and their mobility. In a metal it
is assumed that all the outer electrons are free to carry charge and
the impedance to flow of charge is mainly due to the electrons "bumping"
in to each other.

Insulators however have tightly bound electrons so that nearly no


electron flow occurs so they offer high resistance to charge flow. So
for conductance free electrons are needed.

What makes the material conductive?


Three simple carbon compounds are diamond, graphite and
polyacetylene. They may be regarded as three- two- and
one-dimensional forms of carbon materials .

Diamond, which contains only bonds, is an insulator and its


high symmetry gives it isotropic properties. Graphite and
acetylene both have mobile electrons and are, when doped,
highly anisotropic metallic conductors.

How can plastic become conductive?


Plastics are polymers, molecules that form long chains, repeating
themselves.
In becoming electrically conductive, a polymer has to imitate a
metal, that is, its electrons need to be free to move and not bound to
the atoms.
Polyacetylene is the simplest possible conjugated polymer. It is
obtained by polymerisation of acetylene, shown in the figure.

Two conditions to become conductive:


I- The polymer consists of alternating single and double
bonds, called conjugated double bonds.
In conjugation, the bonds between the carbon atoms are
alternately single and double. Every bond contains a
localised sigma () bond which forms a strong chemical
bond.
In addition, every double bond also contains a less
strongly localised pi () bond which is weaker.

2-The second condition is that the plastic has to be


disturbed - either by removing electrons from
(oxidation), or inserting them into (reduction), the
material. The process is known as Doping.
There are two types of doping

1-oxidation with halogen (or p-doping).

3x
(CH n ) +
I (CH
2

+
)
n

+ I 3

2- Reduction with alkali metal (called n-doping).


x

(CH n ) + xNa (CH n )

+ xNa

The game offers a simple model of a doped polymer. The


pieces cannot move unless there is at least one empty
"hole".
In the polymer each piece is an electron that jumps to a
hole vacated by another one. This creates a movement
along the molecule - an electric current.

Factors that affect the conductivity


1-Density of charge carriers.
2- Thier mobility.
3-The direction.
4-presence of doping materials (additives
that facilitate the polymer conductivity)
5-Temperature.

Applications
Conducting polymers have many uses. The most documented
are as follows:
anti-static substances for photographic film
Corrosion Inhibitors
Compact Capacitors
Anti Static Coating
Electromagnetic shielding for computers
"Smart Windows"
A second generation of conducting polymers have been
developed these have industrial uses like:
Transistors
Light Emitting Diodes (LEDs)
Lasers used in flat televisions
Solar cells
Displays in mobile telephones and mini-format television
screens

Shield for computer screen


against electromagnetic
"smart" windows
radiation

smart" windows

Solar cell
Photographic Film

Light-emitting diodes

Conclusion
For conductance free electrons are needed.
Conjugated polymers are semiconductor materials
while doped polymers are conductors.
The conductivity of conductive polymers decreases
with falling temperature in contrast to the
conductivities of typical metals, e.g. silver, which
increase with falling temperature.
Today conductive plastics are being developed for
many uses.

Applications of Polymers
 Electronics:

Organic solar cells, organic light-emitting diodes,


chemical and biological sensors, rechargeable batteries, photovoltaic
devices, smart window, electronic shielding, integrated circuit
encapsulation, LCD.
Characteristics: Potentially disposable, flexible, ability to undergo
molecular interactions and produce measurable signals.
 Medical: Heart valves, blood filters, artificial heart, vascular
tubing, drain tubes, dentures, cosmetic surgery, grafting, disposable
syringes, contact lenses.
Characteristics:
Biocompatibility,
selective
permeability,
biodegradable, intoxic and non allergic in human body.

Applications of Polymer
Packaging Materials and Coatings
Polymers combine ease of processing and desirable mechanical properties to be the
material of choice.
Transparent and Optical Materials
Polymers are used as windows, optical fibers, lenses, reflectors, and transparent film
packages.
Biological and Medical Materials
Many examples include: dissolvable sutures, implants, prosthetics, and drug delivery
systems
Fluid Modifiers and Suspension Stabilizers
Very small amounts of polymer can significantly affect the viscosity. For this reason,
guar and other gums are common ingredients in ice cream and other foods. Similarly,
many products employ unique solution characteristics of polymers, including
shampoo, engine oil and super absorbent diapers. Undesirable separation of paint and
health care products is prevented through the addition of a macromolecule, parts of
which are soluble, while other parts are insoluble. Similar characteristics of proteins
are essential for life.

 Agriculture: Preventing soil erosion; increasing plant growth, crop


yield, rate of germination & emergence, water holding capacity of
soil, soil permeability, infiltration rates; reducing irrigation
frequency, fertilizer leaching.
Characteristics: Water-soluble and gel-forming polymers.
 Automobiles: Battery cases, car parts (Trim panels, impact
absorber, radio housing, door outer panel, handle, fog light cover),
lubricants, spark plug wires.
Characteristics: Good specific strength & stiffness, part integration,
ease of processing, corrosion resistance, low density, light weight
and relatively low cost.

 Oceans: Boat hulls, pass anger and naval vessels (navy ships), gas
masks, life saving equipments (life boats, inflatable life boats, life
vests).
Characteristics: Light weight, no corrosion, high strength.
 Building Construction: Pipes and guttering, window and door
profiles, glazing, roofing, sealants and adhesives, cement, insulations,
flooring and building panels, geo membranes, road and sports
surfaces, building reinforcement and bridge boilding.
Characteristics: High strength, low density, light weight, high
thermal insulation and excellent weathering performance.
 Sports: Foot-wear, sports garments, billiard balls, puncture
resistant bicycle tires, bullet proof clothes, golf gloves,
Characteristics: Light weight, elasticity, permeability, higher
stiffness, self lubricating and nonstick surface.

POLYMER PROCESSING
Polymers Compounding
- process involving addition of ingredients such as plasticizers,
fillers, stabilizers, gases and pigments, vulcanizing agents, flame
retardants, etc. to the basic polymer resin before it is processed into
finished products.
Techniques used for processing of polymers
 Extrusion - Two principal components are:
- Extruder consists of a hopper that holds the resin stock and
extruder barrel divided into three sections called feed, compression
and metering zones.
- Die is a piece of steel with the shape of the desired part machined
into it.

 Molding: process of shaping an article from a plastic material


usually by applying heat and pressure or pressure alone in a closed
chamber called mould.
- Compression molding is widely used for thermosetting polymers.
- Transfer molding is generally used for thermosetting plastics.
- Injection molding was developed to achieve high speed molding of
thermoplastics.
- Blow molding is used for manufacturing hollow articles such as bottles
automotive fuel tanks, etc.
 Spinning: process of producing fibers. Three main types of spinning,
-Melt spinning is used for polymers that can be melted easily.
-Dry spinning involves dissolving the polymer into a solution that can
be evaporated.
- Wet spinning is used when the solvent cannot be evaporated and must
be removed by means of chemical means.

 Calendring: process for fast and continuous formation of sheet or


film. Calender usually consists of four highly polished rolls commonly
arranged in Z, I or inverted L shape.

 Thermoforming: process for converting a piece of a thermoplastic


sheet into a deep drawn container (egg carton, ice cream cups etc.). In
this process vacuum or air pressure is applied on thermoplastic sheet
from a compressor. When vacuum is used, the process is called vacuum
forming.

 Casting: Three types of casting:


-Die casting is employed to convert liquid prepolymer into a solid object
of desired shape.
- Rotational casting is a technique of making large hollow objects, even
of complex shapes, usually from polyethylene and related polymer in
the form of fine powder.
- Film casting is used to produce polymeric films and is carried out by two
processes: the chill-roll method and moving endless belt method.
 Coating and printing: involves the application of a thin film of
functional material to a substrate, such as paper, fabric, film, foil or sheet
stock. Examples of different coating operations are-roll coating, blade
coating, curtain coating, extrusion coating and skim coating.
 Foaming: Foamed products can be produced by polystyrene,
urethanes, polymethyl methacrylate and a number of polymers.