ME F213

Materials Science and

Engineering

Polymer

Polymer Chain Lengths

Many polymer properties are affected by the length of
the polymer chains. For example, the melting
temperature increases with increasing molecular
weight.
At room temp, polymers with very short chains
(roughly 100 g/mol) will exist as liquids.
Those with weights of 1000 g/mol are typically waxy
solids and soft resins.
Solid polymers range between 10,000 and several
million g/mol.
The molecular weight affects the polymers properties
(examples: elastic modulus & strength).

What Makes Polymers Unique?

Really big molecules (macromolecules) like polymers
have very different properties than small molecules
Chain entanglement:
Long polymer
chains get entangled with each other.
When the polymer is melted, the
chains can flow past each other.
Below the melting point, the chains
can move, but only slowly. Thus the
plastic is flexible, but cannot be
easily stretched.
Below the glass transition point, the
chains become locked and the
polymer is rigid

Polymers Molecular Shape

Straight and twisted chain segments are generated when the

backbone carbon atoms (dark circles) are oriented as in the
figure above.
Chain bending and twisting are possible by rotation of carbon
atoms around their chain bonds.
Some of the polymer mechanical and thermal characteristics
are a function of the chain segment rotation in response to
applied stresses or thermal vibrations.

Molecular Structures for Polymers

secondary

bonding

Linear

Branched

Cross-Linked

Network

Molecular Structures for Polymers

secondary

bonding

Linear

Branched

Cross-Linked

Network

The physical characteristics of a polymer depend also on

differences in the structure of the molecular chains (other
variables are shape and weight).
Linear polymers have repeat units joined end to end in
single chains. There may be extensive van der Waals and
hydrogen bonding between the chains. Examples:
polyethylene, PVC, nylon.

Molecular Structures- Branched

Linear

Branched

Cross-Linked

Network

Where side-branch chains have connected to main chains,

these are termed branched polymers. Linear structures
may have side-branching.
HDPE high density polyethylene is primarily a linear
polymer with minor branching, while LDPE low density
polyethylene contains numerous short chain branches.
Greater chain linearity and chain length tend to increase
the melting point and improve the physical and mechanical
properties of the polymer due to greater crystallinity.

Molecular Structures Cross-linked, Network

secondary

bonding

Linear

Branched

Cross-Linked

Network

In cross-linked polymers, adjacent linear chains are joined

to one another at various positions by covalent bonding of
atoms. Examples are the rubber elastic materials.
Small molecules that form 3 or more active covalent bonds
create structures called network polymers. Examples are
the epoxies and polyurethanes.

Physical Properties
Linear Polymer

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.

Molecular Configurations for Polymers

For polymers having more than one side atom or group of atoms bonded to the
main chain, the regularity and symmetry of the side group arrangement can
significantly influence the properties. Consider the repeat unit

Stereoisomerism:
H

H
C C

H H
C C

H R
or

C C

H R

H H

R represents an atom or side group other than hydrogen (e.g., Cl, CH3)

head-to-tail configuration

head-to-head

Types of Stereoisomerism configuration:

isotactic all R groups on
same side of chain

syndiotactic R groups
alternate sides

H H H H H H H H

H H H R H H H R

C C C C C C C C

C C C C C C C C

H R H R H R H R

H R H H H R H H

cis/trans Isomerism
Geometrical Isomerism:
CH3

CH3

C C
CH2

CH2
C C

CH2

CH2

cis

trans

cis-isoprene
(natural rubber)

trans-isoprene
(gutta percha)

H atom and CH3 group on

same side of chain

H atom and CH3 group on

opposite sides of chain

Thermoplastics and Thermosets

The response of a polymer to mechanical forces at elevated
temperature is related to its dominant molecular structure.
One classification of polymers is according to its behavior
and rising temperature. Thermoplastics and Thermosets are
the 2 categories.
A thermoplastic is a polymer that turns to a liquid when
heated and freezes to a very glassy state when cooled
sufficiently.
Most thermoplastics are high-molecular-weight polymers
whose chains associate through weak Van der Waals forces
(polyethylene); stronger dipole-dipole interactions and
hydrogen bonding (nylon).

Thermoplastics and Thermosets

Thermoplastic polymers differ from thermosetting
polymers (Bakelite, vulcanized rubber) since
thermoplastics can be remelted and remolded.
Thermosetting plastics when heated, will
chemically decompose, so they can not be
recycled. Yet, once a thermoset is cured it tends
to be stronger than a thermoplastic.
Typically, linear polymers with minor branched
structures
(and
flexible
chains)
are
thermoplastics. The networked structures are
thermosets.

Thermoplastic vs Thermoset
Thermoplastics:
--little cross linking
--ductile
--soften with heating
--polyethylene
polypropylene
polycarbonate
polystyrene

Thermosets:
--large cross linking
--hard and brittle
--do NOT soften with heating
--vulcanized rubber, epoxies,
polyester resin, phenolic resin

Specific Elastomeric Properties

Elastomers, often referred to as rubber. They are excellent for parts
requiring flexiblity, strength and durability: such as automotive and
industrial seals, gaskets and molded goods, roofing and belting, aircraft
and chemical processing seals, food, pharmaceutical and semiconductor
seals, and wire and cable coatings.

Mechanical Properties
i.e. stress-strain behavior of polymers
brittle polymer

plastic

elastomer
elastic modulus
less than metal

Strains deformations > 1000% possible

(for metals, maximum strain ca. 10% or less)

Tensile Response: Brittle & Plastic

Near Failure

s(MPa)

fibrillar
structure

x brittle failure
onset of
necking

near
failure

plastic failure

x
Initial

e
aligned, networked
crosscase
linked
case

crystalline
regions
slide
semicrystalline
case

amorphous
regions
elongate

crystalline
regions align

DEFORMATION OF SEMICRYSTALLINE POLYMERS

Before Deformation

Elongation of amorphous chains

Increase in crystalline thickness

Tilting of chains

Separation of
crystalline
block
segments

Orientation of
chains with
tensile axis

Tensile Response: Elastomer Case

s(MPa)
x brittle failure

plastic failure

elastomer

e
initial: amorphous chains are
kinked, cross-linked.

Deformation
is reversible!

final: chains
are straight,
still
cross-linked

Fracture of Polymer

The fracture strengths of polymeric materials are low relative to those of metals
and ceramics.
Thermosetting Brittle Fracture
Thermoplastic- Brittle & Ductile Fracture
Factors that leads to brittle fracture:
reduction in temperature, an increase in strain rate, the presence of a sharp
notch, increased specimen thickness, and any modification of the polymer
structure.
One phenomenon that frequently precedes fracture in some thermoplastic polymers is
crazing. Associated with crazes are regions of very localized plastic deformation, which
lead to the formation of small and interconnected microvoids.
Fibrillar bridges form between these microvoids wherein molecular chains become
oriented

Thanks