The first man made

polymer

Cellulose
nitrate

Poly(isoprene)

1
Linear Polymer
Physical Properties

Stretch

The chains can be stretched, which causes

them to flow past each other. When released,
the polymer will not return to its original form.
Cross-Linked Polymer

Stretch

Relax
The cross-links hold the chains together.
When released, the polymer will return to it's
original form. 2
Linear polymers with side branches
• Linear polymers are those in which the main backbone is
unbranched.
• The way in which side branches are arranged on linear
polymers (polypropylene) can affect the properties of the
polymer.
• This varying degree of randomness will affect the strength and
melting point of the polymer.
• The less random, the stronger the polymer and the higher the
melting point
• This is because in a more ordered polymer they chains can get
closer together and hence the van der Waal’s forces will be
greater.

3
• Polyethylene is classified into several different categories based
branching and molecular weight.

• Linear polyethylene is much stronger than branched polyethylene, but

branched polyethylene is cheaper and easier to make.

4
 Linear polymers with cross links
• Cross links are covalent bonds that can form
between polymer chains.
• If the number of crosslinks is small an
elastomer (vulcanised rubber) will result.
• If the number of crosslinks is large a hard
inflexible thermosetting polymer will be
produced.

5
 Molecular Structures

• Covalent chain configurations and strength:

secondary
bonding

Linear Branched Cross-Linked Network

Direction of increasing strength

1. Adapted from Fig. 14.7, Callister 7e.

6
 Polymers – Molecular Shape

Conformation – Molecular orientation can be

changed by rotation around the bonds
– note: no bond breaking needed

Adapted from Fig.

14.5, Callister 7e.

7
 Polymers – Molecular Shape
Configurations – to change must break bonds

• Stereoisomerism
H H H H H R
C C C C or C C
H R
H R H H

A A

C C
E E
B D D B
mirror
plane
8
What decides the properties of a
polymer?
• Stronger attractive forces between chains =
stronger, less flexible polymer.
• Chains able to slide past each other = flexible
polymer .
• In poly(ethene) attractive forces are weak
instantaneous dipole - induced dipole, will it be
flexible or not?
• Nylon has strong hydrogen bonds, why does this
make it a strong fibre?
9
• the following molecular structures affect
the overall properties of polymers :-
• chain length, different side groups,
chain branching,stereoregularity,
chain flexibility, cross linking.

10
Longer chains make stronger polymers.

• Critical length needed before

strength increases.
• Hydrocarbon polymers average
of 100 repeating units
necessary but only 40 for
nylons.
• Tensile strength measures the
forces needed to snap a
polymer.
• More tangles + more
touching!!!
11
 Polymer structure
• The polymer chain layout determines a lot of material
properties:

• Amorphous:

• Crystalline:

12
Polymers Temperature No Gaseous
State
More complex
behaviour

Viscoelastic
liquid

Glass
Crystallization Transition
Melting

Semi-crystalline
Glassy Solid
Solid
 Crystalline polymers
• Areas in polymer where
chains packed in regular way.
• Both amorphous and
crystalline areas in same
polymer.
• Crystalline - regular chain
structure - no bulky side
groups.
• More crystalline polymer -
stronger and less flexible.

14
Polymer crystallinity
– What influences the degree of crystallinity
• Rate of cooling during solidification
• Molecular chemistry – structure matters
– Polyisoprene – hard to crystallize
– Polyethylene – hard not to crystallize
• Linear polymers are easier to crystallize
• Side chains interfere with crystallization
• Stereoisomers – atactic hard to crystallize (why?); isotactic,
syndiotactic – easier to crystallize
• Copolymers – more random; harder to crystallize

15
Linear polymers with side branches
• Isotactic • Atactic
– Same side of the linear – Irregular points on both sides
polymer of the linear polymer
– high density, rigid and – Chains of molecules cannot
tough and a high softening get close together, therefore
temp. low density.
– Soft, waxy – little use

16
 Tacticity
Tacticity – stereoregularity of chain
H H H H H H H H
isotactic – all R groups on
C C C C C C C C
same side of chain
H R H R H R H R

H H H R H H H R
syndiotactic – R groups
alternate sides C C C C C C C C
H R H H H R H H

H H H H H R H H
atactic – R groups random
C C C C C C C C
H R H R H H H R
17
 MOLECULAR WEIGHT & CRYSTALLINITY
• Molecular weight, Mw: Mass of a mole of chains.

smaller M w larger M w
• Tensile strength (TS):
--often increases with Mw.
--Why? Longer chains are entangled (anchored) better.
• % Crystallinity: % of material that is crystalline.
--TS and E often increase
with % crystallinity. crystalline
--Annealing causes region
crystalline regions
to grow. % crystallinity amorphous
increases. Adapted from Fig. 14.11, region
Callister 6e.
(Fig. 14.11 is from H.W. Hayden, W.G. Moffatt,
and J. Wulff, The Structure and Properties of Materials,
Vol. III, Mechanical Behavior, John Wiley and Sons, Inc.,
1965.) 4 18
Structure/Property Relationships
Additives Processing conditions
• Processing aids • Injection, cast, extrusion
• Stability enhancement • Time/temperature profiles

Polymer
Performance

Molecular architecture Chemical composition

• Blends • New monomers in the
• Grafts, branching backbone (type, quantity)
• Molecular weight

19
The Effect of Molecular Weight and Degree of Polymerization on Polymers

Effect of molecular weight and

degree of polymerization on the
strength and viscosity of polymers.

20
 Behavior of Polymers

Behavior of polymers as a function of temperature and (a) degree of crystallinity and (b)
cross-linking. The combined elastic and viscous behavior of polymers is known as
viscoelasticity.
21
Volume of Polymers as a Function of Temperature

Specific volume of polymers as a

function of temperature. Amorphous
polymers, such as acrylic and
polycarbonate, have a glass-
transition temperature, Tg, but do not
have a specific melting point, Tm.
Partly crystalline polymers, such as
polyethylene and nylons, contract
sharply while passing through their
melting temperatures during cooling.

22
 Types of Plastics

General terminology describing the behavior of three types of plastics. PTFE

(polytetrafluoroethylene) has Teflon as its trade name. Source: After R.L.E. Brown
23
 Thermal Properties
• Tg (glass transition temperature) – temperature at which a material goes
from a rigid, glass like state to a rubbery state.

• Tm (melting point) – temperature at which a material changes from solid

to liquid state.

• Critical parameter in determining fabrication/molding conditions, end use

application opportunities.

Differential scanning calorimetry (DSC)

measures the energy necessary to
establish a zero temperature difference
between the sample and an inert
substance

24
Crystallinity by DSC

 Experiment Setup
Crystallinity by DSC

 Example: Crystalinity
%Crystallinity  H f  100%
obs
of Polyethylene H f
Table: Heats of fusion of 100%
crystalline polymers
 A comparison
Method of Advantages Disadvantages
Analysis
Differential Fast, easy; You’re probably going Need literature values of
Scanning to use DSC anyway for Tg, etc. heat of fusion for 100%
Calorimetry crystalline polymer for
comparison; thermal
history an issue.

Dilatometry A simple way to measure Pure crystalline specific

polymer crystallinity based on volume must be known.
changes in volume.
X-ray scattering Can determine precise crystal Difficult to analyze data,
structure. determine structure.

Polarized Optical A quick way to see if a polymer is Other factors (like strain
Microscopy crystalline. in the polymer) can
cause birefringence;
difficult to quantify.
Entropy and the Melting Point

- CH2 - CH2 -
Polyethylene
Tm ~ 1350C

- CH2 - CH2 - O -
Tm ~ 650C
Poly (ethylene oxide)

- CH2 - CH2 - -
Tm ~ 4000C
Poly (p-xylene)

Factors that Affect the Tg Chain Stiffness

Chain Stiffness
- CH2 - CH2 - Tg ~ - 800C
Polyethylene
CH3
-

- Si - O - Tg ~ - 1200C
-

CH3
Poly (dimethyl siloxane)

- CH3
- -O- Tg ~ 2000C
CH3
-

Poly (phenylene oxide)

Bulky Substituents
CH3

-
- CH2 - CH - - CH2 - C -
Atactic PP: -10 C

-
-

PVC: 87 C

Tg ~ Tg ~ 1750C
Atactic
1000C Poly(-methyl
styrene)
The Effect of
Atactic Polystyrene
-

- CH2 - CH -

-
- CH2 - CH -
Cross - Linking
Tg ~ 1350C
-

Atactic
Poly(-vinyl naphthalene)

Tg

~ 1450C
Atactic Poly(vinyl biphenyl)
The Effect of Diluents

Polymer + Solvent
or Plasticizer
32
33
34
35
36
37
38
Once strains ~ 1% - 2% are reached,various types of deviations
From ideal behavior are observed;

Glassy polymer or
semi-crystalline polymer
x below Tg Semi-crystalline
x above Tg
polymer

Stress
x
() Rubber

Strain ()
STRESS / STRAIN CHARACTERISTICS OF POLYMERS

Stress to Glassy polymer or

semi-crystalline
break polymer
x below Semi-crystalline
Tg
x above
polymer
Energy to break Tg
Stres
s x
Stress () Rubbe
()
r

E
Strain
Strain () ()

Many of the mechanical characteristics of polymers

that we have just discussed (Eg strength,stiffness, Real stress/strain diagrams are
toughness,yield behaviour) can be determined from much more complicated
Stress/strain measurements.

On the left is shown a stress/strain diagram for a

hypothetical material that obeys Hooke's law all
the way to failure
YIELDING IN SEMI- CRYSTALLINE POLYMERS

Stress

Yield
Point

Strain

Reproduced with permiss-ion from J.

Schultz, Polymer Material Science, Prentice-
Hall, New Jersey, 1974.
 NEWTONIAN AND NON -
NEWTONIAN FLUIDS
NEWTONIAN BEHAVIOUR:  =  ( 
a )

Shear Newtonian
. thinning
 xy  slope = a
fluid ( =
slope)

Shear
MOST POLMER MELTS ARE
stress
SHEAR THINNING
Shear
thickenin
g

Strain
rate
 VARIATION OF MELT
VISCOSITY WITH
STRAIN RATE
ZERO SHEAR RATE
VISCOSITY
5

4
log a
(Pa) 3

0
-3 -2 -1 1 2 3 4
0
log (sec- 1)
SHEAR RATES ENCOUNTERED IN PROCESSING
Compression Injection Spin
moulding Calendering Extrusion moulding drawing

0 1 2 3 4 5
10 10 10 10 10 10

-1
Shear rate (sec )
Molecular Weight and Polydispersity

Molecular Weight
Molar mass (M): mass of 1 mole of polymer, in unit of g mol-1. (Practically
people use molecular weight instead of molar mass.)
M = xMo
where x (or n): degree of polymerization, Mo: molar mass of repeat unit.

Molecular Weight Distribution

With very few exceptions (e.g., some materials of biological origin),
polymers consist of macromolecules with a range of molecular weights.

44
Molecular Weight Averages

To define any arithmetic mean A, let's assume unit volume of a sample of

N polymer molecules comprising: N1 molecules with molecular weight M1,
N2 molecules with molecular weight M2, …, Nj molecules with molecular
weight Mj.
N = N1 + N2 + ··· + Nj

Number-average molecular weight (Mn): "the sum of the products of

the molar mass of each fraction multiplied by its mole fraction".

NiMi
Mn = 
Ni

45
Z-Average Molecular Weight (z stands for centrifuge. German
zentrifuge) M z

Viscosity-Average Molecular Weight

M

Mathematically, Mn  Mw  Mz, here the equality sign holds only for monodisperse
polymers.

The ratios of different molecular weight averages Mw/Mn and Mz/Mw are often
used as characteristics of polymer polydispersity.

For most polymers Mw/Mn: 1.5–2.5

For monodisperse polymer: Mw/Mn = Mz/Mw = 1

46
 FRACTION
ATION
POLMER SOLUTION

COLUMN

Collect fractions.
Measure how much
Polymer is in each
fraction
 SIZE EXCLUSION (OR GEL PERMEATION)
CHROMATOGRAPHY
Schematic diagram depicting the separation
Schematic diagram of an SEC of molecules of different size by SEC.
instrument.
Small Large
Solvent Reservoir Permeating Excluded
Molecules Molecules

Injection Port
Void
Volume
Mixing
Valve
SEC Columns

Pores Bulk
Pump Detectors Movement
of
Solvent

For
Foraagiven
givenvolume
volumeofofsolvent
solventflow,
flow,molecules
moleculesof
ofdifferent
differentsize
sizetravel
traveldifferent
different
pathlengths
pathlengths within the column.The smaller ones travel greater distancesthan
within the column.The smaller ones travel greater distances thanthe
thelarger
larger
molecules due to permeation into the molecular maze.Hence, the large molecules
molecules due to permeation into the molecular maze.Hence, the large molecules are are
eluted
elutedfirst
firstfrom
fromthe
the column,
column,followed
followedbybysmaller
smallerand
andsmaller
smallermolecules.
molecules.
 THE CALCULATION OF MOLECULAR WEIGHT BY
SEC
The Simplest Case where Monodispersed Standards of the Polymer are Available

Area normalized
 wi = 1
Polydisperse

Concentration
Sample wi

Intensity

Monodisperse Elution Volume Vi

Standards

hi
wi =  hi
Exclusion
Selective
Permeation
Log
Molecular Mi Mw =  w i Mi
Weight Total

 Permeation
 1
 Mn =

w
i
Vi
Mi
Elution Volume
a
Schematic diagram depicting the calibration of an SEC [] =  w i [i ] = K  w i M i
instrument.
 HOW DOES SEC SEPARATE MOLECULES ?
Benoit and his coworkers
recognized that SEC separates not
on the basis of molecular weight
but rather on the basis
of hydrodynamic volume of the
Calibration Curves for:
Linear PolyB polymer molecule in solution.

Star-shaped Same solvent

Log PolyA Same temperature
Molecular
Weight
Linear PolyA
M

Elution Volume VAL VAS VBL

In GPC, the concentration by weight of polymer in the eluting solvent may be monitored continuously with a detector.
UV absorption, differential refractometer (DRI) or refractive index (RI) detectors, infrared (IR) absorption and density detectors.

The second category is molecular weight sensitive detectors, which include low angle light scattering detectors (LALLS) and
multi angle light scattering (MALLS).

The resulting chromatogram is therefore a weight distribution of the polymer as a function of retention volume.

The elution volume (Ve) of each standard is divided by the void volume of the column (Vo) and
plotted against the Log10 of their molecular weight
Benoit and co-workers proposed that the hydrodynamic volume, V η, which is proportional to the product of [η]
and M, where [η] is the intrinsic viscosity of the polymer in the SEC eluent, may be used as the universal
calibration parameter.

A plot of log [η]M versus elution volume (or elution time) for a particular solvent, column and instrument
provides a universal calibration curve which can be used for any polymer in that solvent.

By determining the retention volumes (or times) of monodisperse polymer standards (e.g. solutions of
monodispersed polystyrene in THF), a calibration curve can be obtained by plotting the logarithm of the
molecular weight versus the retention time or volume. Once the calibration curve is obtained, the gel
permeation chromatogram of any other polymer can be obtained in the same solvent and the molecular
weights (usually Mn and Mw) and the complete molecular weight distribution for the polymer can be
determined.
 COPOLYMERIZATION
POLYMERIZATION OF TWO OR MORE MONOMERS

Examples:
Poly(ethylene-co-propylene) (EP)
Poly(styrene-co-butadiene) (SBR)
Poly(vinylidine chloride-co-vinyl
®
chloride) (Saran )
Microstructure depends on
method of polymerization Random Copolymers
-A-B-B-B-A-A-B-A-B-A-A-A-B-A-B-B-

Alternating Copolymers
B A AB A A B A
B A B
A -A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-
AB B A B A A
B A R*
AB B A R*
B
A A
B A B A
R* A A Block Copolymers
B
A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-B-A-A-A-A-A-A
Dynamic Mechanical Analysis measures the mechanical properties of materials as
a function of time, temperature, and frequency.

In addition to basic material properties, DMA also quantifies finished part

characteristics, reflecting the important contribution that processing has on end-use
performance.

DMA is commonly used to measure glass transition temperatures and secondary

transitions, orientation caused by processing, cold crystallization, cure optimization,
filler effects in composites, and much more.

DMA provides an accurate measure of material stiffness (modulus) but also other
important mechanical properties such as damping, creep, and stress relaxation.

Dynamic Mechanical Analysis, otherwise known as DMA, is a technique where a

small deformation is applied to a sample in a cyclic manner. This allows the materials
response to stress, temperature, frequency and other values to be studied. The term
is also used to refer to the analyzer that performs the test. DMA is also called DMTA
for Dynamic Mechanical Thermal Analysis.
DMA works by applying a sinusoidal deformation to a sample of known geometry. The
sample can be subjected by a controlled stress or a controlled strain. For a known
stress, the sample will then deform a certain amount. In DMA this is done sinusoidally.
How much it deforms is related to its stiffness. A force motor is used to generate the
sinusoidal wave and this is transmitted to the sample via a drive shaft.

Damping is the dissipation of energy in a material under cyclic load. It is a measure

of how well a material can get rid of energy and is reported as the tangent of the
phase angle. It tells us how good a material will be at absorbing energy. It varies with
the state of the material, its temperature, and with the frequency.
Tensile clamps are designed for uniaxial deformation of films and fibers. In
oscillation experiments, the instrument uses constant and variable methods
to apply a static load that prevents buckling and unnecessary creep

3-point bending, or free bending, is often considered a “pure”

mode of deformation because clamping effects are eliminated.
Sample spans of 5 mm, 10 mm, 15 mm, 20 mm, and 50 mm are
available to accommodate a wide range of sample stiffness and
specimen sizes. A unique low-friction, roller bearing supported
design available on the 20 mm and 50 mm clamps improves
modulus accuracy and reproducibility by accommodating and
accounting for twist or curvature in the test specimen.
 Monomer Chemical Structure Some Monomers that
Ethylene CH2 = CH2 can be Polymerized Free
Tetrafluoro Radically
CF2 = CF2
-ethylene
Monomer Chemical Structure
Butadiene CH2 = CH - CH =CH2
Vinyl Chloride CH 2 = CH
CH 3

-
- Cl
Isoprene CH2 = C - CH =CH2
Cl

-
Cl Vinylidene CH2 = C
Chloroprene Chloride
-

-
CH2 = C - CH =CH2 Cl

CH2 = CH OCOCH3
Vinyl Acetate

-
Styrene CH2 = CH

Methyl COOCH3

-
Methacrylate CH2 = C-CH3

CN

-
Acrylonitrile CH2 = CH

58
 The Elements of
Polymer Microstructure

Linear and Branched

Polymers
(A) Part of a Linear Polyethylene
Molecule
High Density
Zeigler-Natta Polyethylene
Catalysts (HDPE)
Essentially
Ethylene Linear

High Pressure Low Density

Free Radical Polyethylene
Polymerization (LDPE)
Significantly
Branched
- Affects Ability to Crystallize

(B) Part of a Branched Polyethylene

Molecule