CY 3012

Macromolecules:
Technology and Applications

Session 2
 Welcome to the second session!

Wish you
Faithfulness, Wisdom and Hope.
 Short -term-and Long term
mechanical properties
Tensile strength
Modulus

Long-term properties
Creep
Stress relaxation
 Poissons Ratio ()

= -per /

per is the linear strain in the direction

perpendicular to the tensile stress producing the tensile
strain .
 Bulk modulus (K) and
Shear modulus ( G)

K = E/ [3 ( 1-2)]

G = E/ [2 ( 1+)]
 Time Dependent Properties
Creep - Change in strain at constant stress

Stress Relaxation- Change in stress at constant

strain
 Compliance
Modulus = Stress/Strain

Compliance = Strain/Stress

If stress is constant, and strain changes we

observe CREEP, and thus the compliance is
called CREEP COMPLIANCE
 Creep Compliance J(t)

e(t)

t
J(t) = Strain/Stress
= (1/ ) + (2 /) + (3/) +
= J1 + J2 + J3 +
 We can approximate creep compliance of a
particular polymer , J(t), by suitable
expressions

Using them, we can propose the strain which

may happen to a sample during service
 Try it then
A straight rod of polymer is 10 mm in diameter and 1m
long. It behaves in a linear viscoelastic manner with a
tensile creep compliance which can wee be
approximated as : J(t)= (2-e-0.1t) GPa-1 where t is in hours.
The rod is suspended vertically and a mass of 10 kg is
hung from it.
Find the change in length after (i) 1 hour (ii) 10 hours
(iii) 100 hours
 Solution
We know that J(t) = Strain/Stress = (t) /
Or (t) = J(t)

= Force /Area
= Mg/( r2)

= 10 x 9.81/[ x (5x 10-3)2]

= 1.249 x 106 Pa
 (t) = J(t)
Now, for 1 hour,
(1) = J(1)
= 1.249 x 106 ( 2- e -0.1 x1 ) x 10 -9
= 1.37 x 10 -3
= 1.37 mm change in 1m
Similarly, (10) and (100) can be seen as 2.04 and
2.50 mm change in 1m respectively.
 Stress relaxation
If a sample is subjected to a fixed strain,
the stress rises immediately and then falls
(reduces or relaxes)with time.

CONSTANT STRAIN

t
Stress-relaxation modulus
G(t) = (t)/
 Yield and Fracture

Please look into the notes covered in session 1

and then proceed!
 Fracture of Polymers

Fracture strengths of polymers are low compared to

metals and ceramics
Brittle fracture occurs in thermosetting polymers.
Fracture is initiated at stress concentrators (scratches,
notches, etc). Covalent bonds are severed during
fracture
In thermoplastic polymers, both ductile and brittle
fracture are possible. Brittle fracture is favoured at
lower temperatures, higher strain rates, and at stress
concentrators
Brittle to ductile transition often occurs with increasing temperature
 Fracture of Polymers: Crazing

Fracture of glassy thermoplastic polymers often

proceeds through crazing. Crazing occurs when
Localized regions yield, forming an interconnected
array of microvoids. Fibrillar bridges of oriented
molecular chains form between voids.
At high enough tensile loads, these bridges elongate
and break, enabling crack propagation
Crazing absorbs fracture energy and increases fracture
toughness
CRAZE
 Force

b
x
l
 Theories of fracture
1. Griffith Theory
2. Irwin Model

Both assume that fracture happens through

the presence of pre-existing cracks or flaws in
the polymer and are concerned with what
happens near such a crack when a load is
applied.
 Griffith theory is concerned with the elastically
stored energy near a crack.

Irwin model is concerned with the distribution

of stresses near the crack.
 Griffith Theory
When a simple crack propagates under a stress,
the breaking stress is given by:

B = [ 4E*/(l)]
is the free energy per unit area of the surface, E*
is called reduced modulus equal to
E/( 1-2 ) for a thick sheet and equal to E for a thin
sheet where is the Poissons ratio and l is the
crack length
 A long strip of polymer 1 cm wide and 1 mm
thick, with no cracks, is subjected to a tensile
force of 100N along its length. This produces a
strain of 0.3 %. Another strip of the same
polymer is identical except that it has a crack
of length 1 mm perpendicular to its long axis at
its centre. If the free energy per unit area of
the surface is 1500 Jm-2, estimate the tensile
load necessary to break the second strip.
 = E
E = /
= F/A
= 100/(10-5 x 3x 10-3 )

= 3.33 x 10 9 Pa
We know that
B = [ 4E*/(l)]
FB/ A= [ 4E*/(l)]
Or
FB = A[ 4E*/(l)]
Substitution gives FB = 797 N
 Irwins Model
The stress increases near the tips of a crack in
a sheet to which uniform stress is applied .
Near the crack the tensile stress is higher than
the applied stress because the stress within
the crack is zero.

 Irwin Model
Introduced the term stress intensity factor K.
K= (l/2)1/2
Fracture stress is reached when K reaches a critical value called K , the C

critical stress intensity factor, which is a measure of fracture

toughness.
B = Kc[ 2/ (l)]1/2

Comparing the earlier expression for

B with this :
B = [ 4E*/(l)]

= Kc2/(2E*),
Can you prove it?

A common expression is :
G= 2
Where G is called strain-energy release rate.
 Fracture takes place when G is greater than
some critical value Gc, the critical strain
energy release rate. It takes account of all
the energy required to generate a new crack
area!
( Compare with which represents only
energy)
Gc = Kc2/E*
 Irwin-Kies Relationship
Gc = (F2/2B) (dS/dl) S = x/F
Allows us to compute Gc from force F,
thickness B .,and change in S when dl
happens.
More employed expressions are:
Gc = 3x2b3E/128l4

F= [EBb3/ 64 l3)]x
 What is the relationship between F, force and l, length of a crack?

Q A Force
b

If b= 2 cm, thickness = 1 mm, critical energy release rate is 2500

J/m2 and Youngs modulus 3 x 10 9 Pa, calculate the value of
F when l= 1cm.

Ans: F= 79 N
 Crazing..
Region ahead of crack
It is a region of low density than the bulk polymer
It extends typically a few micrometers from the tip
of the crack

Length R of the craze ahead of crack tip

R= /8 ( Kc/cr)2
where cr is called the craze stress

 The tensile fracture stress B for a particular

polymer is found to be 6 x 107 Pa when it
contains a crack of length 1 mm perpendicular
to the axis of stress.

If a craze extends to a distance of 30 m, from

the tip of the crack, calculate the craze stress.
 cr !!!!!
We need

We know that

= K [ 2/ (l)]1/2
B c

Kc = B [(l)/2]1/2; Is nt it?

Also we know that

R= /8 ( Kc/cr)2 Then what could be cr ?????

cr = ( B )/4 (l/R )1/2 ; Substitution gives cr as272 MPa.

 Impact testing
Tests the ability for a sudden impact
Flexed beam impact tests and falling weight
impact tests
The former is further classified into Charpy and
Izod impact
In Charpy the test specimen is held at each end
and is struck at the centre by a hammer
In Izod the specimen is held at one end and
struck at the other end
In falling dart test a circular sample is supported
horizontally and a steel dart is allowed to fall so
that it strikes the centre of the sample.

The standard dimensions are radius = 6 cm;

thickness =2mm and dart tip radius is 1mm.
 Toughness
Toughness is really a measure of the energy a sample can
absorb before it breaks.
Think about it, if the height of a triangle is strength, and
the base of the triangle is strain, then the area is
proportional to strength times strain.

Since strength is proportional to the force needed to break

the sample, and strain is measured in units of distance (the
distance the sample is stretched), then strength times
strain is force times distance.
Force times distance is energy!
 Rubber toughening
Many thermoplastics are brittle when stressed, a property
which limits applications.
A good way of strengthening such polymers is to
copolymerise elastomeric chains during manufacture.
The elastomer chains form separate phases in the solid,
typically 10-20 micrometres in diameter, so that when the
material is strained, crazes form at their surfaces, increasing
the energy needed to break the material.
In other words, the material is toughened. The technique is
known as rubber toughening, and has been applied to a
wide range of polymers.
 While incorporation of 10-25% rubber into rigid
thermoplastics increases the toughness, the
much lower tensile modulus of the rubber
component lowers the stiffness of the product.
The copolymer will be sensitive to all the
chemicals which may attack the rigid chains as
well as the elastomeric chains, so care is
needed when specifying such rubber-
toughened grades in place of a rigid polymer.
 One of the best known examples is ABS
plastic, where PB is grafted onto the styrene-
acrylonitrile chains, so converting a brittle
polymer into a much tougher material.

The method has also been used with PMMA,

high-impact polystyrene etc.
 Macromolecular Processing
We now deal with:
Non Newtonian Fluids
Viscosity Measurement
Melt Flow
Composite Flow etc.
 Everything Flows

The Greek letters on the logo of The Society of Rheology: panta rei
may be translated everything flows.
This phrase (or philosophy) is attributed to the Greek philosopher
Heraclitus of Ephesus (536470 BCE) and is taken from the more
complete quote: Everything flows and nothing abides; everything
gives way and nothing stays fixed.

Rheology deformation and flow

From http://www.aip.org/tip/INPHFA/vol-10/iss-2/p29.html
 Newtons law
Laminar ( streamlined ) flow
The tangential force depends on:
Area of contact between tow adjacent layers (A)
Velocity difference between the adjacent layers (dv)
The distance between adjacent layers (dx)
Hence F A dv/dx

F= A dv/dx
 Dimensions
F A dv/dx

F= A dv/dx

= F/ A (dv/dx)

= F dx/ A dv

= Nm/m2 ( m/s)
= N s m-2
= Pa.s
CGS: 1 Poise = 1 dynes s cm-2 = 0.1 Ns m-2
 For some fluids, viscosity is a constant over a
wide range of shear rates ( Newtonian). The fluids
without a constant viscosity (Non-Newtonian)
cannot be described by a single number. Non-
Newtonian fluids exhibit a variety of different
correlations between shear stress and shear rate.
One of the most common instruments for
measuring kinematic viscosity is the glass
capillary viscometer.
 shear stress


shear rate

According
to
Newton
Non-Newtonian Fluids
Bingham Plastic: sludge, paint, blood, ketchup

Pseudoplastic: latex, paper pulp, clay solns.

Newtonian

Dilatant: quicksand
 Reynold number
DV
Re = ---------------

D = Diameter of a channel through which
a fluid flows
V = Velocity of the fluid
= Density of the fluid
= Viscosity of the fluid
Shows the boundary between laminar and turbulent flow
( Re must exceed 2000 for turbulence)
 Try yourself..
Given that

D= 0.5 cm
Viscosity= 150 Pa s
Density = 1000 kg / m3
Volume output= 250 cm3/s

Can you find the Reynolds number?

 Solution
Since D = 0.5 cm = 0.005 m
The cross sectional area of the channel would be:
r2 = x ( 0.0025)2
= 1.96 x 10 -5 m2
V = Q/A
= (2.5 x 10 -4)/ (1.96 x 10 -5)
= 12.7 m s-1
Reynolds number = ( 0.005 x 12.7 x 1000)/150 = 0.42
 Viscosities of materials
Substance Viscosity
( Mpa s)
Air 10-5
Water 10-3
Glycerol 10
Polymer melts 102-106
 r

Pseudoplastic : shear-thinning fluids

Dilatant : shear-thickening fluids
 n> 1 Dilatants
log n=1 Newtonian
n<1 pseudoplastic
log *
n is the flow behaviour index.
 Shear Thinning and Shear Thickening

shear thinning tendency of some materials to decrease in viscosity

when driven to flow at high shear rates, such as by higher pressure
drops

Increasing shear rate

 Shear Thickening

shear thickening tendency of some materials to

increase in viscosity when driven to flow at high shear
rates
Thermoplastics and thermosetting resins-
Rheology
 MFI
Low MFI means high molecular weight

Partially crystalline polymers have

appreciable latent heat of fusion.
 Constituents
Fiber+Matrix+ coupling agent (or coatings)+ fillers

Lamina
(ply, layers, Charge)

(a) Unidirectional continuous

(b) Bidirectional continuous

(c) Unidirectional discontinuous

Basic Building blocks in fiber-reinforced

composites
(d) Random discontinuous
 Injection Moulding
The principle is to inject molten polymer into a
closed cooled mould where it solidifies to give
the product of desired shape.
Machine
Two units
1. The injection unit
2. The clamp unit ( houses mould)
 INJECTION UNIT

Looks rather like an extruder

A single screw rotates within a close-fitting
heated barrel and converts the polymer feed
into a uniform melt
 Stages in Injection Moulding
Cooled manifold and multiple-cavity mould
 Flow in channels

Consider the flow through cylindrical channel with length

L and radius R, with driving pressure of P and volume
output Q
Shear stress at the walls =
Shear rate at the walls r =
app = =

This is Poiseuille expression!

The driving pressure for extrusion P ( app 8)/ ()
 Cross-section of plastic extruder

Plastics extrusion is a high volume manufacturing

process in which raw plastic material is melted
and formed into a continuous profile.

Extrusion produces items such as pipe/tubing,

window frames etc.
Most screws have these three zones:
Feed zone (Also called solids conveying). This zone feeds the
resin into the extruder, and the channel depth is usually the same
throughout the zone.

Melting zone. Also called the transition or compression zone.

Most of the resin is melted in this section, and the channel depth
gets smaller and smaller.

Metering zone ( Also called melt conveying). This zone, in which

channel depth is again the same throughout the zone, melts the
last particles and mixes to a uniform temperature and composition.
 How it works?
The material enters through the feed throat (an opening near the rear
of the barrel) and comes into contact with the screw.

The rotating screw (normally turning at up to 120 rpm) forces the

plastic beads forward into the barrel which is heated to the desired
melt temperature of the molten plastic (which can range from 200 C
(392 F) to 275 C (527 F) depending on the polymer).

In most processes, a heating profile is set for the barrel in which three
or more independent controlled heater zones gradually increase the
temperature of the barrel from the rear (where the plastic enters) to
the front. This allows the plastic beads to melt gradually as they are
pushed through the barrel and lowers the risk of overheating which
may cause degradation in the polymer.
 Flow Mechanisms
Melting
As the polymer is conveyed along the screw a thin film
melts at the barrel wall.
This is usually by a thin film melts at the barrel wall.
This is usually by means of conducted heat from the
barrel heaters, but could be frictional.
 Total flow = Drag flow- Pressure flow- leak flow
Drag flow =
H = Channel depth
D = Screw dip/diameter
N = shaft speed (rpm)
Barrel
= Flight angle H

D

Barrel

Pitch =D tan
Similarly,
Pressure flow is given by
QP=; is the pressure gradience
Total flow
Q = Qd-Qp- Leak flow (negligible)
However, l, H along with are fixed for a
given temperature and thus,
Q=
 Elastic and Viscoelastic Effects
Die Swell

as a polymer exits a die, the diameter of liquid stream increases by

up to an order of magnitude

caused by relaxation of extended polymer coils, as stress is

reduced from high flow producing stresses present within the die
to low stresses, associated with the extruded stream moving
through ambient air

Dr. Aldo Acevedo - ERC

72
SOPS
 Rheology-Rubbers
Raw rubber
Vulcanized
Influence of ingredients
Cure time
Properties

Blow and Hepburn, Rubber Technology and Manufacture,

Butterworths, London, 1987
Physico-chemical Modification of Rubber

Vulcanization

Cross linking
reinforcement
 Rubber Processing
Mixing
Raw Rubber
Basic ingredients Mill
Compounded Rubber Press
Rubber
Vulcanizing Vulcanized Product
agents Basic tread formulation
Accelerators NR -100
Carbon black -47.5
Activators
Sulphur -3.0
Fillers MBT -0.85
ZnO -5.0
Antidegradants
Stearic Acid -3.0
Cure time -30 min
Temperature -140
 Cross-linking
Enhances
Elasticity
Resistance to solvents
Mechanical properties
 Specific volume
Specific volume of a sample is the sum of the volume actually
occupied by the polymer molecules 0 and the free volume (empty
spaces) f.

= 0 + f

/
f is called free volume fraction fT at tempertaure T (fg at Tg)

fT = fg + ( T- Tg )f
f is called the thermal expansion coefficient of free volume.

f = R - G
 Find the fractional free volume of a sample at
a temperature of 170 degree centigrade if its
fractional free volume at Tg is 0.025. Given
that the Tg is 100 degree centigrade and
thermal expansion coefficient of free volume
is 4.8 x 10-4 K-1.
 There is a logic in the selection of ingredients for
plastics and rubbers

The ingredients should be compatible with one

another :
Homogeneity
Uniform flow (Rheological features)
Better processing
Better product finishing
 Hildebrand solubility parameter ()

Provides a numerical estimate of the degree of

interaction between materials, and can be a
good indication of solubility, particularly for
non polar materials such as many polymers.
Materials with similar values of are
likely to be miscible.
 The Hildebrand solubility parameter is the
square root of the cohesive energy density.
The cohesive energy density is the amount of
energy needed to completely remove unit
volume of molecules from their neighbours to
infinite separation (an ideal gas), which is
equal to the heat of vapourisation divided by
molar volume.


Polymers and compounding ingredients having

closely similar solubility parameter values are likely
to be compatible
Compound design
Look into
Maximum service temperature
Minimum service temperature
Chemical resistance
Principal properties
Processability limitations
Cure system limitations
 Conventional units are (calories / cm3)1/2, or
cal1/2 cm-3/2
SI units are (MPa)1/2 (The unit is one of
pressure as one pascal is a joule per cubic
meter.)
Conversion from the two is by 2.0455
(MPa1/2) = (cal1/2 cm-3/2)
 Substance (SI)
n-Pentane 7.0 14.4
n-hexane 7.24 14.9
Diethyl Ether 7.62 15.4
Ethyl Acetate 9.10 18.2
Chloroform 9.21 18.7
Dichloromethane 9.93 20.2
Acetone 9.77 19.7
Poly(propylene) 8.20 16.6
PVC 9.50 19.5
PET 10.1 20.5
Nylon 6,6 13.7 28 .0
Poly(methyl methacrylate) 9.3 19.0
 Polymerisation strategies
Bulk
Solution
Suspension
Emulsion
 Bulk polymerization
Bulk polymerization or mass polymerization is
carried out by adding a soluble initiator to pure
monomer into liquid state monomer.
The initiator should dissolve in the monomer.
The reaction is initiated by heating or exposing to
radiation.
As the reaction proceeds the mixture becomes more
viscous.
The reaction is exothermic and a wide range of
molecular masses are produced.
 Solution polymerization
Solution polymerization is a method of industrial polymerization.
In this procedure, a monomer is dissolved in a non-reactive solvent
that contains a catalyst.
The reaction results in a polymer which is also soluble in the chosen
solvent.
Heat released by the reaction is absorbed by the solvent, and so the
reaction rate is reduced.
Moreover the viscosity of the reaction mixture is reduced, not
allowing autoacceleration at high monomer concentrations.

Once the maximum or desired conversion is reached, excess solvent

has to be removed in order to obtain the pure polymer
 Suspension polymerization
It is a heterogeneous radical polymerization process that uses
mechanical agitation to mix a monomer or mixture of
monomers in a liquid phase, such as water, while the
monomers polymerize, forming spheres of polymer.
A suspension agent is usually added to stabilize the monomer
droplets and hinder monomer drops from coming together
This process is used in the production of many commercial
resins, including polyvinyl chloride (PVC), a widely used plastic,
styrene resins including polystyrene, expanded polystyrene,
and high-impact polystyrene, as well as poly(styrene-
acrylonitrile) and poly(methyl methacrylate)
 Emulsion polymerization
Emulsion polymerization is a type of radical
polymerization that usually starts with an emulsion
incorporating water, monomer, and surfactant.
The most common type of emulsion polymerization is
an oil-in-water emulsion, in which droplets of
monomer (the oil) are emulsified (with surfactants) in
a continuous phase of water.
Water-soluble polymers, such as certain polyvinyl
alcohols or hydroxyethyl celluloses, can also be used
to act as emulsifiers/stabilizers.
 Living Polymerization

Living polymerization is a form of addition polymerization

where the ability of a growing polymer chain to terminate
has been removed.
This can be accomplished in a variety of ways. Chain
termination and chain transfer reactions are absent and
the rate of chain initiation is also much larger than the rate
of chain propagation.
The result is that the polymer chains grow at a more
constant rate than seen in traditional chain polymerization
and their lengths remain very similar (i.e. they have a very
low polydispersity index)
 Living Polymerization

Michael Szwarc in 1956 found that after

addition of monomer to the initiator system
the increase in viscosity would eventually
cease but that after addition of a new amount
of monomer after some time the viscosity
would start to increase again
Typically, polymerization of styrene with an
alkali metal / naphthalene system in
tetrahydrofuran (THF).
Atom Transfer Radical Polymerization (ATRP)

ATRP is a robust system that has generated much interest

among polymer engineers and scientists in both industry
and academia.

The control of the polymerization afforded by ATRP is a

result of the formation of radicals that can grow, but are
reversibly deactivated to form dormant species.
Reactivation of the dormant species allows for the polymer
chains to grow again, only to be deactivated later.
Such a process results in a polymer chain that slowly, but
steadily, grows and has a well-defined end group (for ATRP
that end group is usually an alkyl halide).
 Reversible Addition-Fragmentation chain
Transfer or RAFT
Reversible Addition-Fragmentation chain
Transfer or RAFT polymerization is one of
several kinds of controlled radical
polymerization.
It makes use of a chain transfer agent to
afford control over the generated molecular
weight and polydispersity during a free-radical
polymerization.
 ASTM
ASTM International, formerly known as the
American Society for Testing and Materials
(ASTM), is a globally recognized leader in the
development and delivery of international
voluntary consensus standards.
Today, some 12,000 ASTM standards are used
around the world to improve product quality,
enhance safety, facilitate market access and
trade, and build consumer confidence.
 British Standards
British Standards are the standards produced
by BSI Group which is incorporated under a
Royal Charter (and which is formally
designated as the National Standards Body
(NSB) for the UK).[1] The BSI Group produces
British Standards under the authority of the
Charter, which lays down as one of the BSI's
objectives to:[2]
 DIN
DIN stands for "Deutsches Institut fr
Normung", meaning "German institute for
standardisation".
 Bureau of Indian Standards (BIS)
The Bureau of Indian Standards (BIS) is the
national Standards Body of India working
under the aegis of Ministry of Consumer
Affairs, Food & Public Distribution,
Government of India.
It is established by the Bureau of Indian
Standards Act, 1986 which came into effect on
23 December 1986.
 Test-II
Contents

Fracture, theories of facture, fracture toughness, crazing,

impact testing of polymers

Rheology, power-law fluids, drag flow and pressure flow of

power-law fluids in simple geometries, measurement of flow
properties
Novel polymer- industrial practices, standards- ASTM, BS, BIS,
DIN, some product manufacturing techniques-comparison
between plastics and rubbers, compound and product
management


Courtesy

* Relevant textbooks, journals and websites

* Research scholars of PSTL, NITC
Good luck and Nice time!

Macromolecules
Connecting molecules.
Connecting minds