27-Mar-15

MOLECULAR WEIGHT OF POLYMERS

Some natural polymers have molecules of same molecular
weight (monodisperse)

Molecular weight of Polymers

Synthetic polymers are polydisperse (different polymer

molecules have different molecular weights) as they have
distributed molecular weights.
Molecular weights are controlled during the synthesis of
polymeric resins.
The properties of polymeric materials are strongly dependent on
the molecular weights.

Properties of Polymers depend on the molecular

weight

Properties of Polymers dependent on the molecular

weight

Almost all properties of polymers have dependence

on molecular weight.
much lower molecular weight ; poor
mechanical property
much higher molecular weight ; too tough to
process
optimum molecular weight ; 15,000 100,000 g/mol

Fig. Softening point of epoxy resin increases with increase of molecular weight

Methods for the measurement of molecular weight

of polymers

Fig. Polymer properties vs Polymer size

Gel Permeation Chromatography

Complete molecular weight distribution of polymers can be determined.

Mass spectroscopy
Colligative properties measurement
Viscosity measurement
Gel permeation chromatography (GPC)

27-Mar-15

Molecular weight distribution

Gel Permeation Chromatograph

GPC can separate complex polymer parts.

Polymer does not contain molecule of the same size and, therefore
does not have a single molecular weight.
Polymer contains large number of molecules- some are big, some
small.
Variation in molecular size and weight is known as molecular weight
distribution (MWD)
MWD exist in every polymeric system and this determines to a
certain extent the general behaviour of polymers.

Molecular weight distribution

Molecular weight distribution

Average molecular weight of polymers is determined.

Two ways of representing molecular weight of polymers:

Number-average Degree of Polymerisation (DPn)

=

Number-Average Molecular weight, Weight-Average Molecular weight

Number-average Molecular weight (Mn)
Consider a sample of a polydisperse polymer of total weight W in which N=total
number of moles; Ni=number of moles of species i (comprising of the same
size); ni = mole fraction of species i ; Wi = weight of species i ; wi = weight
fraction of species i; Mi = molecular weight of species i; xi = degree of
polymerisation of species i
=

=
0

Weight-average Molecular weight (Mw)

=
1

Molecular weight distribution

Example

Weight-average Degree of Polymerisation (DPn)

=
=
0

Suppose that a polymer consists of 103 chains of M1 = 106 g/mol, and 103
chains of M2 = 104 g/mol. Then

Example
A polymer sample containing 50 mol% of a species of molecular weight
10,000 and 50 mol% of species of molecular weight 20,000.
Mn= (0.5(10,000)+0.5(20,000))/1= 15,000
Mw = [(10,000)2+(20,000)2]/(10,000+20,000) = 17,000
Weight average molecular weight is greater than number average molecular weight

27-Mar-15

Polydispersity Index

Example

The ratio of weight-average molecular weight to number-average

molecular weight is called the dispersion or polydispersity index (I).

It is a measure of width of the molecular-weight distribution curve.

Normal values of I are between 1.5 and 2.5 but may range to 15 or
greater.

The higher the value of I , the greater is the spread of the molecular
weight distribution of the polymer.

A sample of PVC is composed according to the following fractional

distribution.
Wt.
fraction

0.04

0.23

0.31

0.25

0.13

0.04

Mean
mol. Wt.
x103
g/mol

11

16

23

31

39

(a) Compute Mn, Mw, DPn and DPW

Solution

Solution

Display data in Table

Using equation
=

Wt. Fraction Mean mol.

(wi)
Wt. (Mi)

wi x Mi

wi/Mi

0.04

7,000

280

0.57 x 10-5

0.23

11,000

2,530

2.09 x 10-5

0.31

16,000

4,960

1.94 x 10-5

0.25

23,000

5,750

1.09 x 10-5

0.13

31,000

4,030

0.42 x 10-5

0.04

39,000

1,560

0.10 x 10-5

19,110

6.21 x 10-5

Total

1
= 16,100
6.21 105

g/mole

Using equation
=

= 19,110 g/mole

1 mer weight of vinyl chloride (C2H3Cl) = 62.5 g/mer

=

16,100 /

=
= 258
0
62.5 /

19,110 /

=
= 306
0
62.5 /

Number of molecules per gram = (6.21 x 10-5) x (6.02 x 1023)

= 3.74 x 1019 molecules per gram

Effect of molecular weight and molecular weight

distribution on Physical and Mechanical properties
High molecular weight increases

Tensile strength
Impact toughness
Creep resistance
Melting temperature

Entanglement of chains

Effect of molecular weight and molecular weight

distribution on Mechanical properties
More entangled the molecules, the more tensile force would be
required to cause them slide.
Narrow MWD results in higher strength than broad MWD.
Impact toughness increases with molecular weight (long chains would
transmit energy along the chain and share over more atoms, resulting
in dissipation of energy through vibrations, minor translations, and
heat).
Entanglement also allow some of the energy transport to other
molecules, resulting in decrease in concentration of energy.
Broad MWD result in poor ability to transmit the energy between the
chains.
Higher MW increases mechanical properties and broader MWD will
decrease the properties.

27-Mar-15

Effect of molecular weight and molecular weight

distribution on Melting point
More entangled the molecules, the more input energy required to get
free movement and melting point increases.
High molecular weight enhances materials thermal stability and
makes them suitable for high temperature applications.
Low molecular weight generally reduces melting point and improve
ease of processing.
Crosslinks increase molecular weight, resulting in increased melting
point and mechanical properties.

Melting
point

Mechanical
properties

Melt Index

Effect of molecular weight and molecular weight

distribution on processing
For some types of processes, a narrow MWD is preferred while in
others broad MWD give better processing.
Narrow MWD means that material will melt over a narrow range of
temperature (same size molecules will require same amount of energy
to cause them to move freely)
Narrow MWD is suitable for injection moulding which depend on
freezing of molten polymer.
Extrusion requires broad MWD.
High melt strength (measure of ability of molten material to be
shaped) is achieved when MWD is broad. The small molecules melt
first and lubricate the entire mass giving some ease of sliding to large
molecules.
Broad MWD lowers effective melting temperature whereas the large
polymers give strength to the melt because of their residual
entanglement.
Bimodal MWD provide ease of processing (UHMWPE).

Length of Polymer chain

A parameter used to describe polymer.

Flow characteristics of the polymer are strongly
dependent on MW and MWD.
A melt index measurement is a very easy
method of assessing the MW of polymers
(commonly used in industry).

= ( )

For a polyethene molecule with Dp = 1000, the molecule

would have a maximum length by:

Definition: It is defined as the mass of polymer, in

grams, flowing in ten minutes through a capillary of a
specific diameter and length by a pressure applied via
prescribed alternative gravimetric weights for
alternative prescribed temperatures.

= .

= 2,450

High melt index indicates a low molecular weight and vice versa.
Melt index gives information about molecular weight but not MWD.
Ease of melting of polymer can also be determined.
High melt index numbers (ease of melting, lower energy input and easy
processing.

Length of Polymer chain

Conformation
The change in shape of a given molecule due to torsion
about single () bonds referred to as change in
conformation.
A polymer molecule can take many different shapes due
to its degree of freedom for torsion about bonds.
Rapid change in conformation
is responsible for the sudden
extension of rubber and high
flexibility of polymers.

Anisotropic nature of polymer chains

27-Mar-15

Shape (Steric) Effects

Effects of the shape or size of the atoms on the properties
of the polymer are called Steric effects.
Steric effects determine properties of polymers
Shape and size of the pendant groups have major effect
on some of the important properties of polymers
Large pendant groups, crystallinity decreases (strength
and thermal properties are lower for such polymers)
But
Pendant groups increase strength because of
interference of the bulky groups of chains.

Shape (Steric) Effects

Aromatic groups are very bulky and cause the steric
hindrance effects
Some pendant groups are flexible such as aliphatic
groups
Aliphatic groups do not inhibit translational, rotational or
flexing movement.
Branched chain polyethene (LDPE) is very flexible
material due to aliphatic side branches despite reduction
in crystallinity.
Aromatic pendant group decreases crystallinity,
increases strength and decreases elongation
whereas Aliphatic pendant groups decreases
crystallinity and strength but do not decrease
flexibility

Effect of Substituent group/bulky groups/pendant groups

Shape (Steric) Effects

Bulky groups hinder the movement of the chains
Hindered movement increase mechanical and thermal
properties similar to intermolecular forces or
entanglements
Influence of Bulky side groups (steric hinderance)
Restrict the movement
of chains

Crystallinity decreases
Net effect determines
properties of polymers
Strength decreases,
elongation increases and
thermal properties
decreases

Strength increases,
elongation decreases and
thermal properties
increases

Shape (Steric) Effects

Pendant groups (aromatic groups) in backbone affects
physical properties considerably.
A stiff backbone results in high strength, impact
toughness and higher thermal properties.

Aramid fibres (Kevlar and Nomex) have aromatic groups

in backbone.
Aliphatic chains are more flexible.

Classification of polymers on the basis of steric effect

Steric structure of chains

Bond rotation
become difficult

Bulky side groups

Increases

CH2 CH2

Decreases

PE

Thermoplastics

CH3

Strength, rigidity,
modulus

PP

CH

CH2
n

Thermoset

Flexibility, elongation,
crystallinity

CH2 CH
n

PS
O CH3
C O
CH2

PMMA

C
CH3

High packing
( increased crystallinity),
decreased elongation, high strength,
High melting points,
good resistance against
solvents and chemcials

Small branches decreases viscosity

and
Improves workability in melt
Long branches increase viscosity,
Increase ductility and low strength

3-D polymers,
Increased strength
and rigidity,
Highly brittle,
No ductility,
Donot melt instead
Degrade and char

27-Mar-15

Geometrical Isomerism/Chain configurations

Polymer Crystallinity

Packing of molecular chains

to produce ordered structure

Isoprene exhibit geometrical Isomerism

Polymers are:

LDPE = 50 % crystallinity

Semi-crystalline

HDPE = 75 % crystallinity

Amorphous

Cis-Isoprene

Natural rubber is cis-polyisoprene

(has elsotmeric nature)

Trans-Isoprene

Any chain disorder or

misalignment (twisting,
kinking, coiling) result
in amorphous regions

Trans-polyisoprene (Gutta Percha)

has rigid nature

Head to Tail and Head to Head or Tail to Tail configurations

Structure in the solid state,

size and shape of crystal and
crystal aggregates

Morphology of polymers

Chain folded model

Polymers have small

crystalline regions which are
dispersed in amorphous
regions
Fig. Schematic drawing of single crystal with regular chain folding

Fringed Micelle Model of Semi crystalline polymer

TEM of single crystal of polyethene

having thickness 10-20 nm and 10 m
long

Multilayered structure

Morphology of crystallites from Polymer melts

Crystalline region

Amorphous region

Morphology of crystallites from Polymer melts

Spherulite structure in natural rubber

Spherulites are similar to grain boundaries in polycrystalline materials.

Spherulites lead to grain
boundaries

PE,PP,PVC,PTFE and Nylon form spherulitic structure when they

crystallise from the melt.

27-Mar-15

Kinetics of Crystallization
Formation of nuclei

Crystallinity

Growth of crystallites ( spheurlites

formation in all direction depending on
external conditions, High supercooling
creates many small crystallites while
crystallization at higher temperature
produces fewer spherulites)

Increases

Tensile strength,
Melting point,
Decreases ductility,
Increase resistance
to dissolution

Determination of crystallinity

By measuring
specific
volume/densities

Factors controlling degree of crystallinity

1. Rate of crystallization

Increasing crystallinity of polymers

after solidification

2. Controlling chemistry
3. Side groups

Pre-deformation by
Drawing

4. Tacticity

Heat treating

DSC

c= density of 100 % crystalline material

NMR

a= density of 100 % amorphous material

XRD

s= density of unknown sample

5. Branching
6. Cross-linking

Heat Distortion Temperature, HDT

Thermal Transitions in Polymers

Heating polymer

Polymer chains move internally to absorb energy input

Maximum structural use temperature ,

especially for any application in which
the part will be loaded mechanically
weight

Molecular twisting, vibrating, stretching, translation and other movement

Heat distortion
temperature, HDT

Hard
Stiff
Glass like
Limited
atomic
movements
small
volume
increases

Glass transition
temperature,Tg

Moderately
hard and stiff
Creep
Slightly
higher atomic
movements
Small
volume
increases

Melting
point, Tm

Pliable,
leathery
Larger,
longer-range
and
coordinated
movements

HDT is not formal thermal transition

HDT is easier to determine than Tg

Degradation

Liquid
Entire
polymer
molecules
move
independently

Chain
breakage
Gas release
Char
formation
Dramatic and
non-reversible
change in
properties

Height gauge
Thermometer

Stirrer

Sample dimensions
= 5 x x inch

Heat transfer
fluid

sample

ASTM, D648, Deflection under load test to determine heat distortion temperature

Color change

Limit for
structural
applications

Glass Transition Temperature

Decomposition
temperature, Td
Increasing
temperature

The thermal transition that occurs when the

polymer
molecule
begins
to
make
coordinated long-range movements is called
glass transition temperature (Tg). Polymer
becomes pliable and leather like.

Measurement of Glass transition temperature

2. Differential Scanning
Calorimetery
DSC monitors heat effects associated with phase transitions and
chemical reactions as a function of temperature

Chain
mobility
increases

Tg

1.By measuring changes in specific

volume with temperature

Tg is a temperature at which
frozen free volume of 2.5 %
appears and stays constant at
low temperature

Chain
mobility
freezes

Increase in
temperature

In DSC difference in heat flow to the sample and a reference at

same temperature is recorded as a function of temperature. The
difference in heat flow can be positive or negative.

27-Mar-15

DSC curve
Determination of Crystallinity by
using DSC curve

% Crystallinity =

Enthalpy of the Sample

100
Enthalpy of the totally crystalline sample of same material

The integral under the DSC

peak , above the base line,
gives the total enthalpy
change for the phase
transition

Factors effecting glass transition temperature

Multiple Transitions
Gamma transitions
took place due to the
presence of certain
side groups ( may
increase toughness
of polymer)

Bulky side
groups

Double chain bond or

aromatic groups

Polar side
groups

Tg = 0.5-0.8 Tm (K)

Molecular weight
Crystallinity
Tg of different vinyl polymers

Branching and
crosslinks
Polycarbonate

Melting is simply the process of a polymer chains

gaining sufficient energy to move independently

Melting of polymers
Thermoplastic (Amorphous)
HDT

HDPE Tg = -90 oC

Decomposition temperature, Td

General behaviour of thermoplastics and thermosets

Tg

Hard, stiff

LDPE Tg = -110 oC

Gamma
transition ,
T= -100 oC

Thermoplastics decomposition occur

in liquid state release gas and may
form crosslinks.

Td

Tm

Leathery

Thermosets decomposition occur in

solid state forming char ( by product
of gases are often released and the
polymer may begin to change color,
often yellowing or blackening.

Liquid

Thermoplastic (crystalline)
HDT

When input energy has localized in the bond

and equals the bond energy (breaking of
covalent bonds occur), the corresponding
temperature
is
called
decomposition
temperature.

Tm

Processing Temperature this is

a temperature at which plastic
material can be conveniently
molded TP = Tm + 50 to 100 oC

Measurement of decomposition temperature

Hard , stiff

Liquid

Char

Thermosets

TGA
HDT

Hard, stiff

Tg

Non-thermal energy inputs

energy input from mechanical source
or from any other sources (sound ,
light, x-ray)

Td

Td

Tm

Sample is progressively heated

and changes in the weight of the
material are recorded

DSC or DMTA
TGA ( easier and
most commonly used
method)

Semi-rigid
Temperature

Char

27-Mar-15

Thermogravimetric analysis
Onset of degradation

Differential thermal analysis (DTA)

Changes in sample which lead

to absorption or evolution of
heat can be detected relative
to the inert atmosphere
Schematic illustration of DTA cell

exothermic

TGA curve of a polymer

Diffusion in Polymers
Permeability and absorption characteristics related to the degree to
which foreign substances diffuse into the material.
Penetration of these foreign substances can lead to swelling and
chemical reactions with the polymer molecules, which often leads to
degradation of material and loss of physical properties.
Diffusion rates are greater through amorphous substances than
crystalline.
Size of foreign molecule affect the diffusion process. Small and inert
molecules diffuse faster.
Diffusion in polymers according to Ficks law is defined as

DTA curves

Diffusion in Polymers
Applications requiring low permeability rates:
Automobile Tires and inner tubes, beverage and food packaging.
Application requiring high permeability rates:
Polymer membranes used as filter to separate one chemical from
another (desalination of water)
Polymer electrolyte fuel cells.

J = diffusion flux of a gas through the membrane (cm 3 STP)

PM = Permeability coefficient = DS, (D= diffusion coefficient and S= solubility of
diffusing species in polymer
x = Membrane thickness
P = Difference in pressure of gas across the membrane

Example Problem

Mechanical and Thermomechanical Behaviour of Polymers

Stress-strain behaviour
Brittle (thermosets and some thermoplastics)
Ductile (thermoplastics)
Totally elastic (elastomers)

27-Mar-15

Deformation of Semicrystalline Polymers

Mechanical and Thermomechanical Behaviour of Polymers

Effect of temperature on mechanical properties

Mechanism of Elastic deformation

Elongation of the chain molecules from their stable conformation in
the direction of the applied stress by bending and stretching of the
strong chain covalent bonds.
Some displacement of adjacent molecules resisted by
intermolecular forces.
Elastic modulus is combination of the moduli of crystalline and
amorphous phases.
Elastic deformation in polymers occur at low stress level.

Decrease in modulus
Reduction in tensile strength
Increase in ductility

Effect of rate of deformation

Slower deformation result in decrease in modulus, decrease in
strength and higher elongation.

Deformation of Semicrystalline Polymers

Stages of Elastic deformation

Deformation of Semicrystalline Polymers

Mechanism of Plastic deformation
Interactions between lamellar and intervening amorphous regions in
response to applied tensile load.
Two adjacent chain-folded
lamellae and interlamellar
amorphous material before
deformation
Tilting of lamellar chain folds
during second stage

Separation of crystalline
block segment
Two adjacent chain-folded
lamellae and interlamellar
amorphous material before
deformation

Elongation of amorphous tie

chains during the first stage
of deformation

Increase in lamellar crystallite

thickness (which is reversible)
due to bending and stretching of
chain in the crystallite
Orientation of block segments and tie chains with the tensile
axis in the final deformation stage

Deformation of Semicrystalline Polymers

Heating specimen at
some arbitrary stage of
deformation will allow
material to regain
spherulitic structure and
also shrink (depends on
the annealing
temperature and also the
degree of deformation)

Deformation of Semicrystalline Polymers

Macroscopic deformations of polymers

Methods of increasing strength of polymers:

Molecular weight , Degree of Crystallinity, predeformation by drawing,
heat treating

10

27-Mar-15

Elastomers
Criteria for polymer to be called as Elastomers
Rubber like elasticity (ability to bounce back)
Ability to undergo large deformations and then elastically spring back to
original form
Ability to spring back arises due to light cross-linking between the
molecular chains.
Highly amorphous and composed of cross-linked chains that are highly
twisted, coiled and kinked.
Chain bond rotation must be relatively free for the coiled chains to
readily respond to an applied force.
The onset of plastic deformation must be delayed.
Elastomer must be above glass transition temperature.
Properties: Low elastic modulus and vary with increase of strain. Nonlinear stress-strain curves.

Deformation of Elastomers
Highly coiled, twisted and
cross-linked chains

Chains straighten up upon application of

tensile force

Disordered chain
(High entropy)

Ordered chain
(low entropy)

Increase in Temperature

Driving force for elastic deformations

Entropy (measure of degree of disorder within the system)
Elastomer experiences rise in temperature and modulus increases with
increase of temperature unlike to metals.

Elastomers

Comparison between Vulcanised and Unvulcanised rubber

Vulcanisation
The process of crosslinking in elastomers is called vulcanisation.

Cross linking of natural rubber (cis-isoprene)

Useful elastomer is obtained by reacting 1 to 5 parts of sulphur with 100

parts of rubber (1 crosslink for every 10 to 20 repeat units)

Unvulcanised rubber with very few cross links is soft, tacky and has poor
resistance to abrasion.
Modulus of elasticity, tensile strength and resistance to degradation by oxidation
are enhanced by vulcanisation.

Types of Elastomers

Types of Elastomers

Aliphatic Thermoset elastomers

Synthetic Polyisoprene or Isoprene rubbery (IR)

These
These
These
These

are the most common elastomers.

have a double bond after polymerization has occurred.
are noncrystalline.
are highly flexible.

Natural rubber (extracted from tree)

Produced to meet the shortage of natural rubber during WW.

Mixture of both cis and trans molecular form.
Used for tire for light weight vehicles such as bicylces and early automobiles.
Natural rubber is used extensively because of its low cost.

Butadiene rubber (BR)

No cis or trans isomers

Lower mechanical strength because of no pendant methyl group but also more
flexibility
Lower cost (all synthetic from cheap monomer)
Improvement of low-temp flexibility
Compatibility with other polymer materials
Poor oil resistance and sensitivity to oxidation and UV radiation.

11

27-Mar-15

Types of Elastomers

Example Problem
How much sulphur must be added to 100 g of polyisoprene rubber to cross
link 5 percent of the mers? Assume all available sulphur is used and that
only one sulphur atom is involved in each cross linking bond.

Oil resistant elastomers

Nitrile Butadiene rubber (NBR)

Copolymerization of butadiene and acrylonitrile

More expensive than SBR or BR
Excellent oil and oxidation resistance.
Has good abrasion resistance but poor low temperature elasticity.
Typical applications include: oil and fuel lines, gaskets, seals, conveyor belts and
coatings for printer rolls.

MW (polyisoprene) of mer unit = 68 g/mol

Mole of polyisoprene = 100 g/68 g/mol = 1.47 mol of polyisoprene
For 100 % cross-linking with sulphur we need 1.45 mol of S or

CRChloroprene rubber (neoprene)

1.47 mol x 32 g/mol = 47 g of sulphur

Thermal stability
Non-flammable
Applications : fuel hoses, boots, shoe soles, and coatings for fabrics where oil
resistance and nonflammability are important.

For cross-linking 5 percent of the bonds we need only

0.05 x 47 g = 2.35 g of S

Types of Elastomers

Types of Elastomers

Thermoplastic elastomers

Thermoplastic elastomers

Copolymers such as SBR and SIS are thermoplastic elastomers

Not cross linked.

Noncrystalline.
Aliphatic.
Ease of processing and recycle able
More temperature sensitive.
Not well developed.

Ethylene Propylene Monomer rubber (EPR)

Amorphous
Improved oxidation resistance and improved acid and alkali resistance over
natural rubber but have poor compatibility with other rubbers, poor creep
resistance, relatively poor resilience and poor resistance to hydrocarbon solvents.
Applications: bumpers, hoses, seals, mats, wire insulation , appliance parts ,
gaskets and coated fabrics.

Different forms of degradation of polymers

Types of Elastomers
Silicones

Degradation
(An Irreversible process leading to a significant change in
the structure of a material, typically characterized by a
loss of properties and/or fragmentations)

Stabilization
(The protection of polymeric materials
from which lead to deterioration of
properties)

Photo-degradation
(Degradation preceded by light (UV)

Photo-stabilization
Screening radiation
Absorption of radiation
Radical Scavenging

Poly dimethyl siloxane

Three forms--- oil, elastomers, moulding compound, sealants, adhesives

Oils are used as mould releases, coolants, lubricants, hydraulic fluids, etc.
Silicone elastomers have high molecular weight and crosslinked chains.
Much higher molecular weights than former are called silicone moulding
compounds.
Advantages of silicone elastomers and moulding compounds: Low surface
tension, nonionic/nonpolar characteristics , hydrophobicity, high thermal stability
(250 C) , oxidation resistance, high degree of flexibility at low temperatures, room
temperature curing (RTV),etc.
Biomedical implants and tubing ,etc make excellent use of its superior
biocompatiblity.

Bio-degradation
(Degradation processes in which at least
one step is mediated by biological agents)

Thermal Degradation
(Degradation caused by heat and
temperature)

Bio-stabilization
Chemical inertness
Coating of anti-microbial agents

Thermal Stabilization
Flame Retardancy
Introduction of thermal stabilizers

Ultrasonic Degradation
(Degradation caused by Ultrasonic sounds)
High Energy Degradation
(Degradation caused by high energy
radiations like X-ray, ,, rays)

High Energy
Introduction of radiation protectors

12

27-Mar-15

Polymer Additives/Compounding ingredients

Types of Additives

Functions of Additives

Fillers

Facilitate processing without degradation or decomposition

To cater the requirements of a specific application.

Functions:
Improvement of physical properties.
Making the material cost less.

Desirable Properties of Additives

Additives can be solids, liquids or rubbery materials.
Stable under the processing conditions and also under the conditions of their
applications.
Efficient, i.e, small quantity should do the required job.
Compatible i.e, non-bleeding
Non-toxic and not impart any taste and odour to the polymer and should not
negatively effect the inherent properties of the polymer
Cheap.

Fillers may be organic or inorganic, mineral, natural or synthetic in nature. They may
be particulates, fibrous, resinous or rubbery materials.
Examples, addition of saw dust or wood flour in phenol formaldehyde.
Reinforcing Fillers
Improve the mechanical properties of the polymer.
Can be called as composites.

Types of Additives
Plasticisers and softeners

Types of Additives
How Plasticisers work?

Functions:
Improvement in ductility/flexibility
Reduce glass transition temperature.
External Plasticisation
Addition of glass micro-spheres bring about plasticisation effect by acting as a
spacer between the molecules of the polymer.
Internal Plasticisation
Incorporation of polymer molecules in the polymer so that they become part of the
polymer structure.
Addition of various types of esters can bring about internal plasticisation effect.
Examples trioctyl phosphate, phthalic acid ester , etc.

Types of Additives

Types of Additives

Anti-aging Agents

Antistatic agents

Functions:

Functions:

To minimise the structural changes (chain rupture, cross-linking, chromophoric

groups, polar groups) occur due to chemical reactions such as oxidation, ozone
effect, UV light attack ,etc.
To increase the service life of polymers

To stop the build up of electrostatic charges on the surface of polymeric materials

which can lead to fire and dust catching.

Antioxidants (thiobisphenol,alkylphenol), UV-light abosrobers (hydroxybezophenone)

etc are added.

Compounds such as fatty amides, quaternary ammonium compounds, glycol

esters and sulphates are very common agents. They are usually incompatible
with the polymer due to which they slowly migrate to the surface and give a
protective layer.
Polyethylene glycol is a very widely used antistatic agent for PVC conveyor belting.

13

27-Mar-15

Types of Additives

Types of Additives
Lubricants and flow promoters

Blowing agent

Functions:

Functions:
To produce cellular polymers (foams,sponges)
Blowing agent at the manufacturing temperature turn to a gaseous form to pervade
the mass of the polymer.

To prevent sticking of the polymer to the metal walls.

External lubricants have low solubility and carbon chain length C 22-C32. Examples
are stearic acid, myristic acid, paraffin wax, etc.
To improve the flow of the polymer melt.

Common blowing agents are azo-dicarbonamide (for PVC and polyolefins)

which decomposes at 190-230 C giving off N2, CO and CO2 gases.

Internal lubricants remain within the mass of the polymer reduce the cohesive forces
of the molecular interfaces and thus improve the flow of polymer melt. Examples are
stearyl alcohol, metal stearates, monoglycerin esters, etc.
To reduce friction in the final products.
MoS2 and graphite are added in small quantities (1-2 %) to reduce friction in
applications such as nylon gears and bearings, etc.

Types of Additives

Types of Additives

Colourants

UV-degradants

Functions:

Functions:

To give aesthetic appeal.

To give a means of identification.

To facilitate the disposal of the polymers after they have been used.
Photodegradants

Four methods of imparting colours to Polymers

Coating the surface
Dyeing the surface
Incorporation of the materials which would provide chromophoric groups in the
polymer

On absorbing light, the heat generates a highly reactive chemical intermediate which
destroys the polymer.
Iron di-thio-carbamate is an example of such an agent. The photo activator reduces
the molecular weight of the polymer below 9,000 at which polymer becomes
biodegradable.

Colourant fall into two groups- dyes and Pigments

Polymer
Dyes give colour by dissolving in the polymer (much better against fading but
sensitive to light)

P* (reactive intermediate)

Polymer of lower mol. wt

UV-radiation

Pigments disperse throughout the mass of the polymer (tend to migrate more)

Liquid Crystal Polymers

LC polymers have liquid crystalline state
LCP have ability to be aligned in highly ordered configuration
As solids form domain structures having characteristics intermolecular
spacing.
Partially crystalline aromatic polyesters based on p-hydroxybenzoic acid
and related monomers.
LCP have outstanding mechanical properties at high temperatures,
excellent chemical resistance, inherent flame retardancy and good
weatherability.

Liquid Crystal Polymers

LCP are used in LCDs on digital watches, televisions, monitors, etc.
Cholestric LCPs are used for LCDs as they are liquid at room
temperature, transparent and optically anisotropic.
LCPs are sandwiched tween two glass sheets. The outer surface is
coated with conductive film. The characters are etched into the film on the
side to be viewed. Application of voltage will cause disruption in the
orientation of the LCPs molecules resulting in darkening of the LCP
material and in the formation of a visible character.

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Fracture in Polymers
Thermoset have brittle fracture

Fracture in Polymers
Crazing

Thermoplastic experience both ductile and brittle fracture

Brittle fracture occurs due to

Reduction in temperature
Increase in strain rate
Presence of notch in the sample
Any modification in polymer which increases glass transition temperature
Some thermoplastic experience crazing
Formation of microvoids, growth and coalescence
results in crack formation

Fracture in Polymers
Thermoset have brittle fracture
Thermoplastic experience both ductile and brittle fracture

Brittle fracture occurs due to

Reduction in temperature
Increase in strain rate
Presence of notch in the sample
Any modification in polymer which increases glass transition temperature

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