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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.
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).
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
Branched macromolecule
Ring macromolecules
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.
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.
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.
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.
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.
A fiber -
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
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
0.8
0.9
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
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
L = N d s in
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)
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
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,
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.
3x
(CH n ) +
I (CH
2
+
)
n
+ I 3
+ xNa
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
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:
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.
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.