Chain Flexibility

How easily the main chain of the

polymer can move, is a key factor in
determining the properties of the
material.

Factors affecting chain flexibility:

Temperature
Types of bonds
Side groups
Branching

Chain Flexibility - Temperature

Polymer chains are not static, they are
constantly vibrating and rotating.
How much space or free volume there is
around the chains determines ,how much they
can move.
The more thermal energy (heat) present,
the more the chains will move and the more
space between them. The more flexible the
material.
Each material has a specific temperature at
which the chains are mobile enough that the
material behaves more like a rubbery solid
than a glassy solid. This is the Glass Transition
Temperature (Tg)

Chain Flexibility Types of Bonds

Single Carbon Carbon (C-C) and Carbon Hydrogen (C-H) bonds move relatively easily.
Double Carbon bonds (C=C) do not rotate
and are very rigid.
Having an Oxygen or a Nitrogen in the main
chain provides additional room for movement
because of the lower number of bonds present
for these atoms.

Chain Flexibility Types of Bonds

Having a benzene ring in the main chain can
add stiffness to it.
For example: Polycarbonate has two benzene
rings in the main chain separated by a Carbon
with two methyl groups (CH3) attached. This
structure is very rigid. Polyester Has a benzene
ring in the main structure, but also has an
Oxygen and a few Carbon-Hydrogen bonds to
allow it to be flexible when there is adequate
room to move.
PET

PC
Rigid

Flexible
when hot

Chain Flexibility Side Groups

Side groups restrict chain movement. The
larger the side group, the more rigid the
molecule.
Having a Methyl (CH3) group attached to
one side of the main chain will add some
stiffness. Polypropylene is relatively flexible
even at room temperature.

the

Having one attached to both sides of

main chain will add a lot of stiffness.
PMMA is very rigid.

Chain Flexibility Side Groups

Having a Benzene ring attached to one
side of the chain will greatly affect the
stiffness. Polystyrene is very stiff to the point
of being brittle (CD cases)

Chain Flexibility Branching

Although branching can increase the
entanglement
of the polymer chains, branching increases the
chain
flexibility.
Larger branches hold the molecules further
apart,
increasing the free volume, giving the
molecules
more room to move.

Based on the structure of the monomer,

Let us
determine some of the polymers
properties like:
Crystallinity
Hygroscopic
Glass Transition
Flammability

hylene
Crystalline Yes only C-H bonds, flexible
no side
groups

Hygroscopic No (not O or N)
Glass Transition Low (-118 C)
Flammability Yes only C-H bonds

pylene
Crystalline Yes only C-H bonds,
flexible side
groups every
other C
Hygroscopic No (not O or N)
Glass Transition Low (-9.44C)
Flammability Yes only C-H
bonds

yrene

Crystalline No (Benzene ring makes it

too rigid)
Hygroscopic No (not O or N)
Glass Transition High (99C)
Flammability Yes only C-H bonds

inylchloride

Crystalline No, rigid (Cl to big to allow)

Hygroscopic No (not O or N)
Glass Transition High (85C)
Flammability No (Cl puts out)

rbonate

Crystalline No, too rigid

Hygroscopic Yes (O)

Glass Transition High (149C)
Flammability No (High number of double
carbon
flame)

bonds will extinguish the

er (PET)

Crystalline Yes, flexible enough

Hygroscopic Yes (O)

Glass Transition Low (68C)
Flammability Yes (only C-H and
C=O bonds)

ide (Nylon 6-6)

Crystalline Yes, very flexible

Hygroscopic Yes (O and N)

Glass Transition Low (57C)
Flammability Varies depending on additives, but
will usually self extinguish because of N

Polymethylmethacrylate
(Acrylic)

Crystalline No, too rigid (dual methyl

groups)
Hygroscopic Yes (O)
Glass Transition High (104C)
Flammability Yes (only C-H and C=O
bonds)

Polyoxymethylene (Acetal or POM)

Crystalline Yes, very flexible

Hygroscopic Yes (O)

Glass Transition Low (-73C)
Flammability Yes (only C and O bonds)

Tg is low for
simple linear
polymers

Tg and Tm
increase with
mer complexity

Basically if a polymers glass transition

temperature is well above (say, 50oC above)
ambient room temperature, the material will
behave like a brittle glassy polymer --- itll be
stiff with low impact resistance.
Conversely, if the Tg is well below room
temperature, the material is what is
commonly termed a rubber or elastomer --soft and easily stretched; and those materials
whose Tg is reasonably close to the ambient
temperature will exhibit plastic material
behavior --- strong and tough with good

Molecular weight of polymers

Related to the length of the
chains
Mechanical properties
with M, but processing
becomes more difficult
Commercial polymers:
large
distribution of
Molecular
weights

Polydispersity index (PDI)

Mw / Mn

-----

----

Gives information about distribution breadth

Highly branched polymers : PDI > 20

Generally (commercial polymers) : 2 < PDI < 20
Mn - can affect brittleness, flow and
compression
properties of the polymer.
Mw -related to strength properties, and
impact
resistance

Molecular Weight/Physical Property

Property/Process Effect of
Effect of
Correlations
s
High MW
Low MW
Parameter

Impact Strength

Melt Viscosity

Processing Temp

Brittleness

Drawability

Softening Temp

Melt Flow

Polymer Additives
Mechanical, chemical, physical Properties can be
modified by additives:
Fillers
Improve tensile and compressive strengths, abrasion
resistance,
toughness, and thermal stability
sand, glass, clay, talc (eg. carbon in tires)
Particle sizes range from very small (10 nm) to large
(mm)
Plasticizers: small molecules which occupy positions
between polymer chains (increase distance and
interactions between chains)
increases flexibility, ductility, and toughness
reduces hardness and stiffness
Stabilizers
UV resistance of C-C bonds
Oxidation resistance

Structure parameters affecting polymer properties:

Increase of the chain length.
Effect: increase of tensile strength and Modulus of Elasticity (stiffness).
Increase of number and length of side chains.
Effect: increase of tensile strength and stiffness.
Introduction of large monomers in molecules.
Effect: increase of stiffness.
Increase of number and strength of cross-links.
Effect: increase of tensile strength and stiffness.
Orientation of the molecules as a result of deformation during manufacturing.
Effect: anisotropy of the material properties (properties along the deformation
differ from those in other directions).

CLASSIFICATIONS OF
POLYMERS
According to

origin

Mechanical
response
to elevated
temperature

Stress strain Molecular

Polymerizatio
behavior
characteristics reaction

1- origin

Natural polymers

Synthetic polymers

A) Natural Polymers
Proteins polyamides of polypeptides
polyisoprenes
e.g. rubber and gutta-percha
polysaccharides
e.g. starch , cellulose, agar and

poly nucleic acids such as DNA

and RNA.

B) Synthetic Polymers

Produced in the
laboratory by chemical
reactions. e.g. Acrylic
resin ,nylon and
polystyrene.

Mechanical responce
To elevated
temperature

Thermoplastic
polymers

Thermosetting
polymers

Stress strain behavior

Brittle polymes

Plasticpolymers

Elastomers

Molecular
characteristics

shape

size

chemistry

structure

Molecular
characteristics

1- shape

Straight

bent

twisted

zegzag

Molecular
characteristics

2- size

Large polymer
(high molecular weight)

Small polymer
(low molecular weight)

Molecular
characteristics
3- chemistry

homopolymer
All monomers of
the same type

copolymer
Monomers of tow or more
different types
Random copolymer

Block copolymer

Alternating copolyme
Graft copolymer

Molecular
characteristics

4- structure

Network
linear

branched

Cross linked

CLASSIFICATIONS OF POLYMERS

According to

origin

Mechanical
response
to elevated
temperature

Stress strain Molecular

Polymerizatio
behavior
characteristics reaction

5- polymerization
reaction

Condensation
reaction

Addition reaction