UNIT-1 Polymers-Basics and Characterization

Syllabus

Basic concepts: monomers, repeat units, degree of polymerization, linear,

branched and network polymers, classification of polymers, Polymerization:
condensation, addition, radical chain, ionic and coordination and
copolymerization. Average molecular weight concepts: number, weight and
viscosity average molecular weights, polydispersity and molecular weight
distribution Measurement of molecular weight: end group, viscosity, light
scattering, osmotic and ultracentrifugation methods, analysis and testing of
polymers.

Monomer: -

A polymer is any of a class of natural or synthetic substances composed of very

large molecules, called macromolecules, which are multiples of simpler
chemical units called monomers.

Monomers are thus building blocks of polymers. All simple molecules cannot
behave as monomers but only those with two or more bonding sites can act as
monomers. Thus, molecules like ammonia, water, ethanol etc are not
monomers. Alkenes, vinyl chloride, adipic acid, glycol with two bonding sites
act as monomers.

S.NO Monomers Polymers

1 Ethylene Polythene

2 Propylene Polypropylene

3 Butadiene Polybutadiene

4 Tetrafluoroethylene Polytetrafluoroethylene

5 Vinyl chloride Polyvinyl chloride

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Degree of polymerisation (DP): -
The number of repeating units in a polymer chain is called
degree of polymerization (DP). The properties of polymers are
different from those of its monomers.
Molecular weight of polymer = Molecular weight of monomer
x DP Polymers with high DP are called high polymers while the
polymers with low DP are called oligopolymers.
The molecular weight of high polymers ranges from 10,000–
10,00,000. Polymers may be natural (e.g., cellulose, proteins,
natural rubber, wool and silk) or synthetic (e.g., polythene,
PVC, Teflon, nylon and
Bakelite).

Classification of Polymers

1.Bsed on occurrence, 2. Based on structure, 3. Based on morphology 4. Based

on usage

1.Bsed on occurrence(source)

Polymers are again divided into three subcategories:

1. Natural polymers: They are found naturally in plants and animals.

Resins, starch and rubber are examples of this.
2. Semi-synthetic polymers: This is a modified version of natural rubber;
rubbers are treated with chemicals to make them semi-synthetic.
Cellulose acetate and cellulose nitrate are examples that come under this
subcategory.
3. Synthetic polymers: Polymers which are completely man-made are
called synthetic polymers. Polythene, Nylon 66, and synthetic rubber are
the widely used synthetic polymers.
2. Based on structure

There are three different types polymers, based on their structure:

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 1. Linear polymers: They consist of a long and straight-chain of
monomers. PVC is a linear polymer
2. Branched polymers: They are linear polymers containing some
branches. Low-density polythene is an example.
3. Network or cross-linked polymer: Polymers having cross-linked bonds
with each other is called cross-linked or network polymer. Generally,
they are formed from bi-functional or tri-functional monomers. Bakelite
and melamine are examples of this type of polymer.
3.Based on morphology

A. Crystalline
In which molecule folding in regular
Eg: nylon, polyester, High density polymers
B. Amorphous
In which molecule chain folding in random
Eg: polystyrene,PMMA

4. Based on usage

hey are again classified into four subgroups.

1. Elastomers: Polymers that are rubber-like solids and have elastic

properties. Here, the polymer bonds are held together by weak
intermolecular forces and that allows these polymers to stretch. The
cross-links present in the polymer between the chains help to retrace the
original position after the removal of the applied force. Examples are
Buna-s and Buna-s.
2. Fibres: They are polymers having strong intermolecular forces like
hydrogen bonding. Due to this strong force, molecules are kept closer,
that is, they are closely packed. Because of this property, they are
crystalline in nature. Polyamide and polyesters are examples.
3. Thermoplastic polymers: These are the liner or slightly changed to
branched polymers that can be softened on continuous heating and
hardened on cooling. Their intermolecular force lies in between the fibres
and elastomers. Polyvinyls, polystyrene etc., are examples of
thermoplastic polymers.
4. Thermosetting polymers: These polymers come under the category of
heavily branched or cross-linked, which can mould on heating and can’t
regain the original shape. So, these cannot be reused. Bakelite is an
example.

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 POLYMERISATION
The chemical reaction by which the monomers are combined to form
polymers is called polymerisation

Types of Polymerisation
(i) Addition polymerisation
(ii) Condensation polymerisation
(iii) Co-polymerisation

(i) Addition Polymerisation (or) Chain Polymerisation

In addition polymerisation, several bifunctional monomers
combine to form polymers by addition reaction without the
elimination of any byproducts. The monomers containing
double bonds generally undergoes addition polymerisation and
produce linear polymers. The produced polymer contains the
same elemental composition as that of the monomer. The
molecular weight of polymer is an integral multiple of the
monomer.
e.g. 1. Polymerization of vinyl chloride

2. Polymerization of ethylene

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 3. Polymerization of styrene

(ii) Condensation Polymerisation (or) Stepwise Polymerisation:

In condensation polymerisation, the polymer is formed by
stepwise reaction between the same or different polar groups
containing monomers with the elimination of small molecules
like H2O, HCl and NH3. Polymerisation proceeds through
intermolecular condensation and forms linear or cross-linked
polymers. The molecular weight of a polymer is not an integral
multiple of the molecular weight of monomers.
e.g., 1. Nylon-6, 6

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 2. Polyester

(iii) Co-polymerisation
When two or more different types of monomers undergo
simultaneous polymerisation, it is called co-polymerisation. The
properties of copolymer are different from those of individual
monomers. The copolymers may be alternating, random block
and graft copolymers.
e.g. Nylon-6,6

BUNA-S:

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  Free Radical Polymerization:-
A free Radical Polymerization is a polymerizing approach by which successive
addition of free radicals takes place to form a polymer unit. It is a type of chain-
growth polymerization, with a cationic, anionic and coordination
polymerization. Free Radical Polymerization occurs in three steps, i.e.
Initiation, Propagation and Termination.
Free Radical Polymerization is an essential technique for obtaining different
polymers and material composites. It was used to get 40 billion of 110 billion
polymers in the United States in 2001.
Mechanism of Free Radical Polymerization
Free Radical Polymerization occurs in three steps, i.e.

 Initiation of Free Radical

 Propagation of Free Radical
 Termination of Free Radical
Initiation of Free Radical
Initiation is the foremost step in the polymerization process. An active centre is
generated in this process to begin polymerization. All the monomers are not
liable for the initiation process.

 One or two radicals are created from the initiating molecules in the first
step.
 Radicals are transferred from the initiating molecules to the monomer
units in the second step.

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Propagation of Free Radical
A polymer spends most of its time expanding its chain length or propagating.
After initiation of free radical, it attacks another monomer subunit. It uses one
of the pi bond electrons to form a stable bond with another carbon atom. The
other electron returns to the second carbon atom, turning the whole molecule
into a radical.
After initiation, the chain propagates until no monomer is left or termination
starts.

Termination of Free Radical

Termination is the final step in the polymerization process. Termination occurs
in different stages. If longer chains are expected, the initiator concentration
should be less; otherwise, many short chains will form.

 Ionic polymerization

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Sivaprasad Bonala, Assistant Professor-GIT
1. Number average molecular weight ( ):

It is defined as and the ratio of total weight of the polymer molecule and
total no.of molecules, assume that there are no .of molecule is a polymer
sample n1 of these have M1 molecular weight.Therefore ,the number of
molecules present in polymers
n1+n2+-------ni
The weight of n1 molecules = n1 M1
The weight of n2 molecules = n2 M2
The weight of ni molecules = ni Mi

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2 . Weight average molecular weight ( ):

It is depends upon the mass of the groups of the molecules having particle
molecular weight in this average process the molecular weight of each group of
molecule is multiplied by the weight of the species sample and and dividing the
total mass of the polymer it is denoted by Mw the weight of n1 molecule of have
molecular weight M1.

n2 them having molecular weight = M2

n3 them having molecular weight = M3
ni them having molecular weight = Mi

weight of n1+n2+-------ni molecule = n1 m1 , n2 m 2 , n3 m 3 , ----------- ni mi

Weight average molecular weight ( ):

Weight average molecular weight ( ):

Weight average molecular weight ( ):

3. Viscosity average molecular weight ( ):

One of the ways to measure the average molecular weight of polymers is viscosity
of solution. Viscosity of a polymer depend on concentration and molecular weight
of polymers. Viscosity techniques is common since it is experimentally simple.

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Viscosity average molecular weight ( ):

1/a
Viscosity average molecular weight ( ):
Where a = mark

Polydispersity :

 Figure: Molecular weight distribution of two hypothetical polymer

samples having same number average molecular weight but different
polydispersities.
 Polydispersity gives an idea of the lowest and highest molecular weight
species as well as the distribution pattern of the intermediate molecular
species.
 To know a polymer property, we must have a knowledge of the
both the average
 molecular weight and its dispersion pattern. This dispersity with respect to
the lowest to
 the highest molecular weight homologues is expressed by a simple
molecular weight distribution curve. Such a curve for a polymer
sample is computed by plotting the number fraction (ni) of the
molecule having a particular molecular weight(Mi) against the
corresponding molecular weight.
 in general a simple chemical compound tiny's particle each of which has
the sample molecular weight this is system is called a mono dispersibility
system but in this case polymer each which case have different molecular
weight of the system is called a poly dispersibility system this is
represented by the following figure.
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 m
n
n Sample 1

n
Sample 2
n
n

End Group Analysis:

 The end group analysis is a chemical method used to determine the number
average molecular weight of a polymer sample through the analysis of
reactive functional groups at one end or both end
 e.g. Carboxyl terminated polybutadiene, hydroxyl terminated
polybutadiene. Apart from hydroxyl and carboxyl groups, other end groups (
aldehyde, amino, ester) can possibly be present in various polymers.
 For detecting and analyzing quantitatively functional end-groups of linear
polymer (nylon), the amino end-groups of nylon dissolved in m-cresol are
readily determined by titration with a methanolic perchloric acid solution.
 Other titratable end groups are the hydroxyl and carboxyl groups in
polyesters and the epoxy end groups in epoxy resins. The sensitivity of this
method decreases as the molecular weight increases.
 This method is limited to the determination of polymers with a molecular
weight of less than about 20,000.
 Methods: End group analysis, viscometry, light scattering and osmotic
pressure From the knowledge of functional group equivalent and
functionality, the molecular weight can be calculated using the following
equation

Mn =

Viscosity method :
The molecular weight obtained by this technique is the viscosity average
molecular weight, Mv.. The viscosity of a polymer solution is considerable
high as compared to that of pure solvent. The increase in viscosity by the
macromolecules in a solution is a direct function of the hydrodynamic
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 volume and hence the molecular weight of the macromolecules.
The relationship between viscosity of a polymer solution and molecular
weight is given
by Mark-Houwink equation-
[η] = KMa

Where [η] is the intrinsic viscosity, M- molecular weight and a and K are
constant for a particular polymer/solvent/temperature system. Values of K
and a are available for mayknown polymers.
For a polymer type of known K and a values what is required is the
determination of theintrinsic viscosity using the above equation.
For unknown polymer systems, the K and a values are generated by
fractionating the polymer sample into several fractions and for each
fraction the molecular weight is determined by Osmometry or light
scattering method and corresponding intrinsic viscosity is measured.

Light Scattering Method:

Light scattering methods to determination of weight average molecular

weight, Mw. When polarizable particles are placed in the oscillating electric
field of a beam of light, the light scattering occurs. Light scattering method
depends on the light, when the light is passing through polymer
solution, it is measure by loses energy because of absorption, conversion
to heat and scattering. The intensity of scattered light relies on the
concentration, size and polarizability that is proportionality constant which
depends on the molecular weight.

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 For light scattering measurements, the total amount of the scattered light is
deduced from the decrease in intensity of the incident beam, I0, as it passes
through a polymer sample. This can be described in terms of Beer’s law for the
absorption of light

Osmotic method:-

Membrane Osmometry is absolute technique to determine Mn. The

Solvent is separated from the polymer solution with semi permeable
membrane that is strongly held between the two chambers. One chamber is
sealed by a valve with a transducer attached to a thin stainless steel diaphragm
which permits the measurement of pressure in the chamber continuously.
Membrane Osmometry is useful to determine Mn about 20,000-30,000 g/mol
and less than 500,000 g/mol. When Mn of polymer sample more than
500,000 g/mol, the osmotic pressure of polymer solution becomes very
small to measure absolute number average of molecular weight. In this
technique, there are problems with membrane leakage and symmetry.
The advantages of this technique are that it doesn’t require calibration and it
gives an absolute value of Mn for polymer samples.

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 Since osmotic pressure is dependent on Colligative properties, i.e., the
number of particles present, the measurement of this pressure
(Osmometry) may be applied to the determination of the osmotic pressure
of solvents vs. polymer solutions.

The difference in height (h) of the liquids in the columns may be converted
to osmotic pressure (π) by multiplying the gravity (g) and the density of the
solution (p), i.e., π = hpg.

In an automatic membrane osmometer, the unrestricted capillary rise in a

dilute solution is measured in accordance with the modified Van’t Hoff equation:

The reciprocal of the number average molecular weight (Mn ) is the intercept
when data for
π /RTC vs. C are extrapolated to zero concentration.

Ultracentrifugation method:-

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  It is a one of the method for molecular weight determination using the
centrifugal force to separate the suspended particles from the liquid
 polymer molecule is a solution used a subjected to very high centrifugation
force and settle down the segmentation rate of the polymer molecule setting
down under the influence of the constitution and centrifugal force is related
to molecular weight making use of these particles two methods are adapted
for the molecular weight determination

1.Sedmentation velocity method

In this method the solution is subjected to very high gravitational fluid. this process
is affected by an ultra centrifugation which can be provide spin's as high as 65000
revaluation per minute due to high centrifugal force the polymer molecules until
start segmentation

By applying stokes law it is possible to correlated sedimentation coefficient

Where SO,DO the segmentation, diffusion constant denoted by the extra floating the
segmentation coefficient(S) and diffusion coefficient(D) at the different
concentration zero concentration.

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A homogeneous solution of non concentration is taken and subjected to ultra
centrifugation has the segmentation comins a boundary both the solvent face and
the solution face until be formed

Has interpreciation process these boundary both the solvent and solution face
slowly

Receipts away from the axis of rotation usually the moment of the boundary is
maintained by the taking photograph or by UV detection at suitable intervals from
a times the rate at which the boundary moves is the segmentation velocity it is be
calculated using the following equation

U=

X1 and X2 are the distance of the boundary from the rotation axis at a time t1 and t2

The segmentation coefficient yes is related to the segmentation velocity by the

equation

S=

Segmentation constant is not can be computed by the extra floating yes value for
the difference concentration zero concentration according to the equation.

Diffusion coefficient d can be simultaneously calculated by the measuring the

concentration gradient at different times using the refractive index as measured of
concentration

Diffusion coefficient for different concentration or measured and extra ported to

zero concentration to obtain the not as per the equation.

Ks and Kd are the constants for the given polymers solvent system
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2.Sedmentation equilibrium method

In this method a thermodynamic equilibrium is achieved by practically equilising

the sedmentation and diffusion velocity is for attaining equilibrium state the
ultracentrifugation has to be at the lower rate for a longer period it is take several
days to attend equilibrium state during this the centrifugation spins in kept at
around 15,000 RPM under the centrifugal force and equilibrium concentration
gradient is established along the cell and the macro molecules get distributed
according to the molecular weight.

At equilibrium the molecular tendency to diffuse into the place concentration Jones
is balanced by the opposing tendency of polymer molecules to segment this at this
days the segmentation and diffusion balance out the molecular weight is given by
the equation

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Weight is obtained by the weight average molecular weight Ca and Cb are the
concentration values in the cell at distance X1 and X2 from axis of rotation.

The macro molecules or distributed in the centrifugal cells according to their

molecular size the segmentation equilibrium method can be used to get a molecular
weight distribution of a Homogeneous system.

Drawback: laborious and the consuming.

Polymer Testing and Analysis

 Polymer analysis and testing employs both physical and analytical methods
to verify the chemical, mechanical, and thermal properties of a polymeric
material. These properties are instrumental in making sure that the polymer
part will perform as required by the end user.
 For example, we can verify if the parts are the proper material using FT-IR,
check for contamination using DSC, and then determine if the parts are
degraded using the melt flow indexer. Additionally, mechanical tests such as
durometer hardness, izod impact, tensile, and flexural strength are useful in
determining the mechanical integrity of a part.
 We perform polymer testing and analysis by using our FT-IR to determine
the composition of organic thin films, surface contamination, fibers or
composites. Additionally, thermal characterization can assist in determining
performance, process capabilities, quality, and aid in product development.
Polymer Testing and Analysis Capabilities

1. Flammability:

 Test the flammability of each kind of polymer listed below by holding it in a

flame for 5 to 10 seconds and then remove it from the flame. Hold the
sample over an asbestos pad to catch any drips. Work in or near a fume hood
and try to direct as many of the fumes as possible into to the fume hood.

2. Tensile Test Capabilities

 A variety of equipment models are used to test specimens in all sizes, from
small fasteners to large tubing and bolts. Our tensile testing lab has machines
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 with load capacities from 8 oz. to 600,000 lb. Elevated temperature tensile
testing is also offered to 1800°F.

3. Color Gloss Testing

 The color and gloss of a product can be affected by various environmental

factors. In addition to the accelerated weathering exposure needed to
simulate environmental damage (Xenon, UV, Abrasion, Thermal), ATS
performs color and gloss testing to determine the resulting visual change to
the coating. Our environmental testing lab measures these variations
quantitatively by using a spectrophotometer.

4. Polymer Analysis Technology(FTIR)

 Combined with these techniques provides significant complementary data

regarding a polymer molecule's molecular structure. FTIR, when used
together with other analytical techniques, can prove very effective in the
identification of unknown plastics and polymeric materials.

5. Melt Flow Rate

 The melt flow rate is an indirect measure of molecular weight, with high
melt flow rate corresponding to low molecular weight. Synonyms of MFI
are melt flow rate and melt index, which are commonly abbreviated: MFR
and MI. When the volume of the extsrudate is measured, the melt volume
rate is reported.

6. Thermal Cycling & Heat Aging

 Test products can be evaluated for functionality during or after extreme

exposure through thermal cycling. Typical observable adverse effects
include warping, discoloration or texture change.
7. Dielectric Strength/Breakdown

 Dielectric strength is measured as the maximum voltage required producing

a dielectric breakdown through a material. It is expressed as Volts per unit
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 thickness. For a plastic material the dielectric strength varies from 1 to 1000
MV/m.
8. Flexural Strength Testing

 Applied Technical Services performs flexural strength testing to verify the

amount of force a polymeric material can support before it gives out.
 Manufacturers choose design materials based on several performance
characteristics, many of which contribute to the final assembly’s overall
durability.
 They understand that verifying the material’s expected strength can mean
the difference between a successful product and one that can suffer an
unexpected, premature failure.
 While unacceptable in all cases, such a situation proves specifically
dangerous in the case of a load-bearing structural element designed to
withstand perpendicular stresses.

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