Pendahuluan

Plastic Products
Plastics can be shaped into a wide
variety of products:
Molded parts
Extruded sections
Films
Sheets
Insulation coatings on electrical wires
Fibers for textiles

Polymer Science and Processing

Technology
Successful product design requires a knowledge of:
the requirements of the final product
the behaviour of polymeric materials
commercial polymer processing technology
relevant cost and market factors.

At the heart of polymer science and

technology is molecular structure. It
dictates not only final product properties,
but polymer synthesis and processing
methods.
9

Polymer Classification: Terminology

While we have
chosen an
applications
perspective on
polymer
classification,
many alternate
schemes are
widely used.
These are usually
composition/prop
erty specific, as
opposed to
applications
oriented.

J.S. Parent

10

Definisi & Klasifikasi

Polimer

Polymers: Introduction
Polymer: High molecular weight molecule made
up of a small repeat unit (monomer).
A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A

Monomer: Low molecular weight compound that

can be connected together to give a polymer
Oligomer: Short polymer chain
Copolymer: polymer made up of 2 or more
monomers
Random copolymer: A-B-B-A-A-B-A-B-A-B-B-B-A-A-B
Alternating copolymer: A-B-A-B-A-B-A-B-A-B-A-B-A-B
Block copolymer: A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B

Polymer
Poly

mer
many

repeat unit (building blocks)

repeat
unit

repeat
unit

H H H H H H
C C C C C C
H H H H H H

H H H H H H
C C C C C C
H Cl H Cl H Cl

Polyethylene (PE)

Poly(vinyl chloride) (PVC)

repeat
unit

H
C
H

H H
C C
CH3 H

H H
C C
CH3 H

H
C
CH3

Polypropylene (PP)

Carbon chain
backbone
14

Types of Polymers
Polymer Classifications

Thermoset: cross-linked polymer that cannot be

melted (tires, rubber bands)
Thermoplastic: Meltable plastic
Elastomers: Polymers that stretch and then return to
their original form: often thermoset polymers
Thermoplastic elastomers: Elastic polymers that can
be melted (soles of tennis shoes)

Polymer Families

Polyolefins: made from olefin (alkene) monomers

Polyesters, Amides, Urethanes, etc.: monomers linked
by ester, amide, urethane or other functional groups
Natural Polymers: Polysaccharides, DNA, proteins
15

Common Polyolefins

Monomer
Ethylene

CH3
Propylene
Ph
Styrene

Polymer

Polyethylene

Polypropylene

Polystyrene

CH3

H3C

Vinyl Chloride
F2C CF2
Tetrafluoroethylene

CH3

CH3 CH3 CH3 CH3 CH3 CH3 CH3

Ph

Ph

Ph

Ph

Cl
Poly(vinyl chloride)

Repeat unit

Cl

F3C
Poly(tetrafluoroethylene): Teflon

Cl
F2
C

C
F2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

CH3

Ph

F2
C

Ph

Ph
CH3

Cl

C
nF
2

Cl
F2
C

C
F2

Cl
F2
C

C
F2

CF3

16

17

18

Polyesters, Amides, and Urethanes

Monomer
HO2C

CO2H

Terephthalic
acid
O

Polymer
O

OH

HO
Ethylene
glycol

Poly(ethylene terephthalate

HO

Nylon 6,6

O
CO2H H2N

HO2C

NH2

1,4-Diamino
benzene

Terephthalic
acid
H2
C

OCN

NCO

4,4-diisocyantophenylmethane
O
HO

H
N

H2
C

Kevlar

HO

Ester
O

NH2
OH H2N
4
1,6-Diaminohexane

H2 H2
O C C O H

HO

HO
4
Adipic Acid

O
4

N
H

N
4
H
Amide
O

H
n

H
N

H
N H
n

OH
HO
Spandex
Ethylene
glycol
O
H2 H2
H
N
O C C O H
n

Urethane linkage

19

Monomer

Isoprene
H OH
HO
HO

Natural Polymers

Polymer

Polyisoprene:
Natural rubber

HO

H OH
H

OH
H
H
-D-glucose

OH

Poly(-D-glycoside):
cellulose

Polyamino acid:
protein

R
Amino Acid

O P O
O

O
O

H3N

OH
Nucleotide
Base = C, G, T, A

Base
oligonucleic acid
DNA

OH

OH
H

H
N

R1
DNA

HO

O
HO

O
H3N

Rn+1

H
N
n

OH
Rn+2

O
O P O

O
O

DNA

Base

20

Rubbers

21

Polymer Classification
Polymers are commonly classified based
on their underlying molecular structure.
Polymers

Thermoplastics
Crystalline Amorphous

Elastomers

Thermosets

Polymer Classification:
Thermoplastic/Thermoset
One of the most practical and useful classification of polymer
compounds is based on their ability to be refabricated.
Thermoplastic: polymers that can be heat-softened in order to
process into a desired form.
Polystyrene, polyethylene
recyclable food containers

Thermoset: polymers whose individual chains have been

chemically crosslinked by covalent bonds and therefore resist
heat softening, creep and solvent attack.
Phenol-formaldehyde resins, melamine paints
permanent adhesives, coatings
26

Thermoplastics and
The response ofThermosets
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 dipoledipole interactions and hydrogen bonding (nylon).
27

Thermoplastics and
ThermoplasticThermosets
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.
28

Examples of Thermoplastics

29

More Examples of Thermoplastics

Polymer

PTFE

http://www2.dupont.com/Teflon/en_US/index.html
http://en.wikipedia.org/wiki/Teflon

Some engineering polymers

(1)

Some engineering polymers

(2)

Some engineering polymers

(3)

Elastomers (1)

Elastomer (2)

Struktur & sintesa Polimer

Polymer Classification: Chain

Architecture

Linear: A linear polymer chain is one without branches. Its actual

conformation may not be line-like, but varies with chain stiffness,
crystallinity and applied stresses.

Branched: Chains with an appreciable number of side-chains are classified

as branched. These side chains may differ in composition from the
polymer backbone.

Crosslinked: A continuous
network of polymer chains is
a crosslinked condition. In effect,
there is just one polymer chain
of infinite molecular weight.

Chain architecture has a dramatic

effect on properties such as
viscosity, elasticity and temperature
stability.

Polymer Classification: Chemical Microstructure

Homopolymers: polymers derived from a single monomer (can be
linear, branched or crosslinked).

poly(ethylene), poly(butadiene).
Random copolymers: two monomers randomly distributed in chain.
AABAAABBABAABBA
poly(acrylonitrile-ran-butadiene)
Alternating copolymers: two monomers incorporated sequentially
ABABABABABABABAB
poly(styrene-alt-maleic anhydride)
Block copolymers: linear arrangement of blocks of high mol weight
AAAAAAAAAAABBBBBBBBBBBBBBBAAAAAAAA
polystyrene-block-polybutadiene-block-polystyrene or
poly(styrene-b-butadiene-b-styrene)
Graft copolymers: differing backbone and side-chain monomers
poly(isobutylene-graft-butadiene)

Copolymers
two or more monomers
polymerized together
random A and B
randomly positioned
along chain
alternating A and B
alternate in polymer
chain
block large blocks of A
units alternate with large
blocks of B units
graft chains of B units
grafted onto A backbone

random

alternating
block

graft

43

Copolymers can be used to tailor functionality or generate new phases and behaviors.

Block copolymer, example:

Poly(styrene)-block-poly(butadiene)

Random copolymer, example:

Poly(styrene-ran-butadiene)

Graft copolymer,

example:
Poly(styrene)-graftpoly(butadiene)

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:
46
polyethylene, PVC, nylon.

Molecular StructuresBranched
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
47
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.
48

Chemistry and Structure of

Polyethylene

Tetrahedral
arrangement
of C-H

Polyethylene is a long-chain hydrocarbon.

Top figure shows repeat unit and chain structures.
Other figure shows zigzag backbone structure.
49

MOLECULAR WEIGHT

Molecular weight, M: Mass of a mole of chains.

Low M
high M

Polymers can have various lengths depending on the number

of repeat units.
During the polymerization process not all chains in a polymer
grow to the same length, so there is a distribution of
molecular weights. There are several ways of defining an
average molecular weight.
The molecular weight distribution in a polymer describes the
relationship between the number of moles of each polymer
species and the molar mass of that species. 50

Molecular Weight Distribution

The distribution of molecular weights within a polymer is
characterized not by a single, unique average, but defined through
a number of different ways.
The number average, Mn,
considers the number of
molecules of each size,
Mi, in the sample:
niMi
Mn
ni
The weight average, Mw,
considers the mass of
molecules of each size
within the sample:
w iMi
Mw
wi

MOLECULAR WEIGHT DISTRIBUTION

M n x i M i
M w w i M i
__
Mn = the number average molecular weight (mass)
Mi = mean (middle) molecular weight of size range i
xi = number fraction of chains in size range i
wi = weight fraction of chains in size range i52

Polydispersity is the term we use to describe the

fact that not all macromolecules in a given sample
have the same repeat number x.
Polydisperse

size

Paucidisperse

Monodisperse

size

size

Even in a pure sample, not all molecules will be the same.

Nature often does better than people do.

MW Requirements of Industrial Polymers

Elastomers
amorphous materials operating above Tg
physical props derived from chain entanglement, crosslinking
Adhesives

range from elastomeric (pressure sensitive) to semicrystalline (hot melt) to glassy (epoxy resins)
Plastics
broad class of materials whose properties are derived from
an amorphous phase and often from a crystalline phase
Fibres
highly crystalline materials
physical properties derived from degree of crystallinity
Coatings
must be applied as a low viscosity medium and cure to
produce satisfactory properties

Composition Distribution
Inclusion of two or more monomers in a material generates a
distribution of composition within, and between, polymer chains.
Changes to material properties can be pronounced:
Chemical properties: fibre dyeability, hot melt adhesive bonding
strength, solvent resistance
Phase transitions: crystallinity, Tg, Tm, phase separation
Mechanical properties: elasticity, modulus, toughness...

Tailored polymers can be developed through consideration of:

the character of incorporated monomers and,
polarity of main chain or pendant functionality
potential for crystallization
their sequence distribution within polymer chains.
random chain composition
alternating
block sequencing
graft structure

Random Copolymers
Materials comprised of a random distribution of different monomers
are the most widely employed industrial copolymers.
Compositions vary from essentially homopolymers to
materials containing equimolar quantities of constituent
monomers, depending on the application.
Compare:
Poly(acrylonitrile), Poly(butadiene) and Poly(acrylonitrile-cobutadiene)
Poly(ethylene), atactic Poly(propylene) and Poly(ethylene-copropylene)
Poly(acrylonitrile) and Poly(acrylonitrile-co-methyl acrylate)

Random Copolymer Phase Transitions

Random incorporation of significant amounts of two or more
monomers generally:
yields a Tg between the two constituent homopolymers.
lowers Tm for crystalline domains, and reduces the extent of
crystallinity.
Shown here is a
generic phase
diagram for a system
of semi-crystalline
monomers.

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).
58

Polymers Molecular Shape

Straight (b) and twisted (c) 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.
59

Polymer Classification: Chemical Class

A popular classification scheme amongst chemists is based on
polymer functionality.
Polyesters:
poly(ethylene terephthalate) - Dacron

Polyamides:

poly(caprolactam) - nylon 6

H O

Urethanes:
carbamate linkages through reaction
of diisocyanates and diols.

C O

N C

H O
N C O

Another (!) classification scheme, again favoured by chemists is

based on differences between the polymer and constituent
monomer(s).
Condensation polymers: synthesis involves elimination of
some small molecule (H2O in the preparation of nylon)
Addition polymer: formed without loss of a small molecule
i.e. ethylene polymerization to generate poly(ethylene)

Alternating Copolymers
Alternating copolymers are essentially -AB- homopolymers.
Condensation polymers are structurally of this class, but are
not considered alternating.
C N

poly(butadiene-ran-acrylonitrile)

C N

poly(butadiene-alt-acrylonitrile)

Alternating Copolymers: Elastomers

Typical stress-strain curves at 0C for unreinforced rubber vulcanizates:
1: poly(propylene-alt-butadiene)
2: natural rubber: cis-1,4polyisoprene
3: synthetic cis-1,4-polyisoprene
4: cis-1,4-polybutadiene
5: poly(styrene-co-butadiene) (25:75)

Segmented Polyurethanes
Schematic morphology of unstretched
semicrystalline polyurethane
copolymer (segmented block copolymer).

A:
hard nylon fibre
B:
bicomponent nylonspandex
C:
mechanical stretch
nylon
CHEE 890

J.S. Parent

D:

Graft-Modified Polyolefins
Functionalization of polymers is a cost-effective means of
developing specialty materials. Grafting of versatile functional
groups to polyolefins can improve blend performance and/or
enhance high-temperature properties.
A leading example is the melt grafting of maleic anhydride to
polyethylene to generate a material that improves adhesion
between polyethylene and nylon phases in toughened nylon parts.

ROOR
O
O

What is the distribution of grafts in the material?

Graft-Modified Materials: Composition Distribution

Silane modified resins are used for enhanced adhesion with
siliceous fillers and moisture curing:
Si(OMe)3
ROOR
Si(OMe)3

Distribution of silane grafts is expected to influence:

coupling efficiency to fillers
crosslink density of cured articles

Polymer Synthesis
There are two major classes of polymer formation mechanisms
Addition polymerization: The polymer grows by sequential
addition of monomers to a reactive site
Chain growth is linear
Maximum molecular weight is obtained early in the
reaction
Step-Growth polymerization: Monomers react together to
make small oligomers. Small oligomers make bigger ones,
and big oligomers react to give polymers.
Chain growth is exponential
Maximum molecular weight is obtained late in the
reaction

Addition Polymerization

In*

A
Initiation

In

A*

Addition Polymerization
Propagation

In*

A
Initiation

In

A A*

Addition Polymerization
Propagation

In*

A
Initiation

In

A A A*

Addition Polymerization

In*

In

Initiation

A A A A*

nA

In

*A
In

A A A A A
A*

In

Propagation

A A A A A*
n

A A A A
m

A A A A A

In

*A

A A A A

A A A A A
n

Combination

B A A A A
m

Chain Transfer
New reactive site
is produced

Disproportionation
Termination
Reactive site is consumed

MW

MW
0

% conversion

100

A A A A A

k propagation
k ter mination

Addition (Chain) Polymerization

Initiation
Propagation

Termination

71

Types of Addition Polymerizations

Anionic

C3H7

Li

Ph

C4H9

Ph

Li+

C4H9
Ph

Ph

PhCO2
Ph

Cationic

Cl3Al OH2

Ph

Ph

Radical

PhCO2

Li+

Ph

Ph

n
H
Ph

HOAlCl3

PhCO2

Ph

H
Ph

Ph

Ph

HOAlCl3
Ph

Step-Growth Polymerization
n

Stage 1

Consumption
of monomer

Stage 2
Combination
of small fragments

Stage 3
Reaction of
oligomers to give
high molecular
weight polymer

Step-Growth Polymerization
Because high polymer does not form until the end of the reaction, high
molecular weight polymer is not obtained unless high conversion of
monomer is achieved.

Degree of Polymerization

1000

Xn = Degree of polymerization
p = mole fraction monomer
conversion

Xn

1
1 p

100

10

1
0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

Mole Fraction Conversion (p)

0.9

Nylon-6,6
O
Cl

O
4

Cl

Adipoyl chloride

H2N

NH2

NaOH
Cl

O
HO

N
H

1,6-Diaminohexane

Adipoyl chloride
in hexane

O
4

O
N
H

Nylon 6,6
Diamine, NaOH, in H2O

N
H

6 carbon
diacid

6 carbon
diamine

Nylon-6,6

N
H

H
n

Nylon-6,6
Since the reactants are in different
phases, they can only react at the phase
boundary. Once a layer of polymer forms,
no more reaction occurs. Removing the
polymer allows more reaction to occur.

Adipoyl chloride
in hexane
Nylon 6,6
Diamine, NaOH, in H2O

Some Common Addition Polymers

Condensation (Step) Polymerization

81

Condensation polymerization (ex.

Polyester)

Some Condensation Polymers

Ancient Polymers
Naturally occurring polymers (those
derived from plants and animals)
have been used for centuries.
Wood
Cotton
Leather

Rubber
Wool
Silk

Oldest known uses

Rubber balls used by Incas
85

Cellulose

Cellulose is a highly abundant organic compound.

Extensive hydrogen bonding between the chains
causes native celluose to be roughly 70%
crystalline. It also raises the melting point
(>280C) to above its combustion temperature.
Cellulose serves as the principal structural
component of green plants and wood.
Cotton is one of the purest forms of cellulose and
has been cultivated since ancient times.
Cotton also serves (along with treated wood pulp)
as the source the industrial production of
cellulose-derived materials which were the first
"plastic" materials of commercial importance.

Rubber

A variety of plants produce a sap consisting of a

colloidal dispersion of cis-polyisoprene. This milky fluid
is especially abundant in the rubber tree (Hevea); it
drips when the bark is wounded.
After collection, the latex is coagulated to obtain the
solid rubber. Natural rubber is thermoplastic, with a
glass transition temperature of 70C.
Raw natural rubber tends to be sticky when warm and
brittle when cold, so it was little more than a novelty
material when first introduced in Europe around 1770.
It did not become generally useful until the midnineteenth century when Charles Goodyear found that
heating it with sulfur a process he called
vulcanization could greatly improve its properties.
cispolyisoprene

Sifat-sifat Polimer

Specific Thermoplastic Properties

Thermoset data

Thermoset Properties

Mechanical properties of
Polymers

Hookes Law

Young's modulus, E, can be calculated by dividing the tensile stress by the extensional strain in the elastic
(initial, linear) portion of the stressstrain curve:
where
E is the Young's modulus (modulus of elasticity)
F is the force exerted on an object under tension;
A0 is the original cross-sectional area through which the force is applied;
L is the amount by which the length of the object changes;
L0 is the original length of the object.

Young's modulus, also known as thetensile modulusor

elastic modulus, is a measure of thestiffnessof anelastic
material and is a quantity used to characterize materials. It is
defined as the ratio of thestress(force per unit area) along anaxis
to thestrain(ratio of deformation over initial length) along that axis
in the range of stress in whichHooke's lawholds.

 Young's Modulus =Stiffness = E =Slope of Stress/Strain Curve

= = E = Slope of Stress/Strain Curve =s / e
The steeper the stress/strain relationship (the higher Young's
Modulus, E), the more stiff the material. Breaking strain and stress
are the amounts of strain and stress observed at the breaking
point. The more ductile the material, the more strain at breakage;
the stronger the material, the higher the breaking stress.
Ductile materials will deform more than stiff materials before
breaking; however, ductile materials are not usually as strong a
stiff materials. Compare, for example, a brittle object, say beach
glass, and a ductile object, perhaps a rubber chicken. Glass may
be strong (high breaking stress) but it is not ductile (low strain
(i.e., little deformation) at breaking). A rubber chicken extends
quite a bit before it breaks (long live rubber chickens) but can not
withstand as much stress.

Stress
Stress is "force per unit area" - the ratio of applied
forceFand cross section-defined as "force per area".
tensile stress- stress that tends to stretch or
lengthen the material - acts normal to the stressed
area
compressive stress- stress that tends to compress or
shorten the material - acts normal to the stressed
area
shearing stress- stress that tends to shear the
material - acts in plane to the stressed area at rightangles to compressive or tensile stress

Strain

Strain is defined as "deformation of a solid due to stress" and

can be expressed as
= dl / lo
= / E
where
dl = change of length (m, in)
lo= initial length (m, in)
= unit less measure of engineering strain
E =Young's modulus(Modulus of Elasticity)(N/m 2(Pa),
lb/in2(psi))
Young's modulus can be used to predict the elongation or
compression of an object.

 For many materials, Young's modulus

is a constant over a range of strains.
Such materials are calledlinear, and
are said to obeyHooke's law.
Examples of linear materials include
steel, carbon fiber, and glass. Rubber
and soil (except at very low strains)
arenon-linearmaterials.

Modulus of Elasticity (Young's Modulus)

Slope of thestress-strain diagramwithin the elastic zone is called
Modulus of Elasticity or Youngs Modulus. This parameter depends
only on the material type.

In this equation E is the Modulus of Elasticity, is the applied stress in psi or ksi within the elastic limit,
and is the corresponding strain. Since strain does not have any units, E has units of psi or ksi. For
structural steel E 29,000 ksi. A smaller modulus of elasticity translates to more a flexible (or less rigid)
member.

Thermal properties

Permeability

Polymer Morphology
The ultimate properties of any polymer
(plastic, fiber, or rubber) result from a
combination of molecular weight and
chemicalrequire
structure.
Polymers
a Mechanical Property
particular MW,
which depends
largely on the
chemical
structure, to have
desirable
Molecular Weight
mechanical

Polymer Morphology
The mechanical properties result from attractive
forces between molecules
dipole-dipole interactions, H-bonding, induction forces,
London forces or ionic bonding, ion-dipole interactions
+

C
dipole-dipole

+ C

O
-

H
N

O
H
N
-

R
H-bonding

C
O

A lower MW polyamide will produce good

fiber properties as compared to the

Polymer Morphology
Hydrogen Bonding
A dipole-dipole interaction for hydrogens
bonded to electronegative elements
Electrostatic Interaction

O
H

O
R

H
O

very important
in cellulose

Weak bond ~ 5 kcal mol-1 (c-c ~ 81 kcal mol-1 )

Require short bond distance ~ 2.5 (c-c ~ 1.46)

Polymer Morphology
Intermolecular forces drop off very rapidly with
distance important polymer molecules be able to
pack together closely to achieve maximum cohesive
strength.
ex. Natural Rubber
unstretched state - molecules are randomly distributed
low modulus
stretched state - molecules become aligned, at 600%
elongation high modulus
(2000 times higher than unstretched)
unstretched - amorphous / stretched - crystalline

Overview
Morphology is a term that has slightly different meaning
depending on the words with which it is used. In
general it has to do with the form or structure of
whatever topic it is used to describe.
For our purposes, we will use it to describe the form or
structure of the polymer chains of thermoplastic
materials when they are in their frozen or solid state.
For thermoplastic resins, there are two basic
morphologies:

AMORPHOUS and SEMI-CRYSTALLINE

Amorphous
Amorphous polymers appear random and jumbled when
allowed to cool in a relaxed state. They appear very
similarly to their molten state, only the molecules are
closer together.
They can be described as being similar to a large pot of
spaghetti noodles.

Semi-crystalline
A portion of the molecular chains in semi-crystalline
polymers tend to fold-up into densely packed regions
called crystals as the polymer cools.
If more than 35% of the polymer chain will form these
crystals the polymer is classified as semi-crystalline.

Semi-crystalline
regions

Amorphou
s regions

Example
Think of Semi-crystalline materials like
ramen noodles. When in their solid state,
they have a compact ordered
arrangement

The dense arrangement makes

them stiffer and they resist flowing
in that state

Example
Amorphous materials are like cooked ramen noodles in that there is a random
arrangement of the molecules and there are no crystals present to prevent
the chains from flowing

It is important to remember
that both materials have the
random, unordered
arrangement when molten

Degree of Crystallinity
There are many different factors that can determine the
amount of crystals or degree of crystallinity of a
plastic component.

Cooling rate it takes time for the polymer chains to

fold up. If we cool the polymer more quickly, we form
fewer crystals

Additives some additives can be put into plastics to

increase the degree of crystallinity while others can
disrupt the formation of the crystals giving us a lower
degree of crystallinity

Polymer type different materials can form higher

or lower levels of crystallinity depending on their
molecular structure

Temperature

As matter heats up, the molecules vibrate faster due

to the addition of the heat energy.
This faster vibration causes the molecules to move
further apart increasing the space or free volume
between the molecules
At some point the molecules get so far apart, they
are no longer solid, they behave like a liquid.
If you continue to heat the matter, the molecules get
so far apart they turn into a gas (evaporate)
With plastic materials, it is very difficult if not
impossible to get them to evaporate because of their
degree of entanglement.

Temperature
For most materials, we are concerned with the melting
point and boiling point. These are the temperatures at
which the matter experiences a change of state
oSolid to Liquid
oLiquid to Gas
For thermoplastic materials, we are concerned with:
oGlass Transition Temperature
oMelting Temperature

Glass Transition Temperature (Tg)

The Tg is important to both morphologies of
thermoplastics
In amorphous materials, it is the temperature at which
the molecules have enough absorbed enough energy and
have moves far enough apart that the material behaves
more rubber-like than glass-like.
The material stretches further when pulled
The material absorbs more impact energy without
fracturing when struck
When the material does fail, it fails in a ductile
manner as opposed to a brittle manner. (If a material
fails in a ductile manner, it yields before it fails. In a brittle
manner, it fails or ruptures before it yields)

Glass Transition Temperature

(Tg)
The sample to the left
experienced a brittle failure
The material did not yield before
failure
The material broke like glass

The sample to the right broke in a

ductile manner
The material yielded (stretched)
before failure
The material behaved more like a
rubber

Glass Transition Temperature (Tg)

Because a semi-crystalline material has a portion of its chain that remains in
an amorphous state, it is also affected by the Tg
- When a S/C material is above its Tg, it can form crystals
below the Tg crystal formation stops

once it

dips

-The amorphous portions of the chains have enough energy and the
molecules are far enough apart, that the molecules can continue to fold up
and unfold.
- The crystals are more easily pulled apart
- The material is more flexible
Ex. Polyethylene and Polypropylene both have low Tgs. They are

way below room temperature. That is why milk jugs and yogurt
containers are flexible when you take them out of the
refrigerator.

Melt Temperature (Tm)

Amorphous materials dont truly have a Tm. They just
continue to soften more until they behave more like a
liquid.
The molecules absorb enough energy and move far
enough apart (increase the free volume) that the material
can flow.
When we refer to the melt temperature for amorphous
materials, it is usually the temperature at which we can
process it.

Melt Temperature (Tm)

For S/C materials, the Tm is the temperature at which the
crystals melt.
Once the crystals are melted the material generally flows
very easily.
The ideal temperature for growing crystals is
approximately 2/3 of the way between the Tg and the Tm.
Not in all cases, but in many, the degradation
temperature for S/C materials is not much higher than the
melt temperature.

Orientation
When we talk about orientation in respect to polymer
materials, we are talking about the alignment of the
molecules.
Think of a polymer molecule like a broken rubber band
sitting on your
desk.
- As it flows, the molecule straightens out and
stretches

Orientation

-When it stops flowing, it wants to return to its random

state.
-As it cools, it will either start to fold up into a crystal
or just move
closer to the other molecules.
-If we cool the molecule quickly, before it has a chance
to relax, we
lock in that molecular alignment or orientation.
-When the molecules are aligned the material is
stronger in the
direction of the alignment, but weaker transverse to
it.

Properties
You have already seen that there is a big difference
between the two basic morphologies of thermoplastic
materials.
These differences cause the different types of materials to
experience property differences.
Although the properties are mainly dependent on a
specific polymers structure, there are tendencies that
go with the specific morphologies.
This is why material selection is so important
to the plastics field.
If the wrong material is used for a specific application, it
can fail and cause damage or worse personal injury or

Properties

Chemical Resistance

Plastic materials are used in virtually every aspect of

todays activities and they come into contact with a wide
variety of chemical substances that they need to resist.
As a general rule S/C materials are more resistant to
chemical attack than amorphous materials.
It is more difficult for the chemical media to penetrate the
dense crystalline structure to damage the polymer
chains.
Polyethylene is used to store everything from detergent to
mineral spirits to gasoline. Polypropylene is only slightly
less chemically resistant than Polyethylene.

Properties

Chemical Resistance

Of the amorphous materials PVC is probably the best in

chemical resistance, mainly due to the large chlorine
atom that helps to protect the main polymer chain.
Polycarbonate, Acrylic, Polystyrene and the other
styrenics are all very susceptible to chemical attack,
especially to mineral spirits and solvents like lacquer
and paint thinners, alcohol, and gasoline.

Properties

Optical Properties

Amorphous materials have a much higher clarity than S/C

materials.
The crystals that form in the material diffract the light as
it passes through giving the material a translucent to
opaque appearance.
If the crystallinity is disrupted by adding a copolymer or
other additive or by quenching the material so quickly the
crystals dont have enough time to form, the material
may appear somewhat clear.
Amorphous Acrylic more commonly known as Plexiglas
and Polycarbonate used in safety glasses and optical
lenses are far superior in terms of optical properties.

Properties

Impact Resistance

The material structure determines the impact resistance,

but as a general rule, S/C materials are more brittle than
Amorphous.
The chain portions that are folded up in the crystal restrict the
polymer chains as they try to move past one another when a
force is applied making the S/C materials more brittle.
Polycarbonate is used in safety glasses, but General Purpose
Polystyrene (GPPS) is very brittle both are amorphous, but
have different polymer structures.
On the S/C side, Polyethylene is very ductile at room
temperature because it is above its Tg, but Nylon and Polyester
are brittle at room temperature.

Properties

Viscosity

S/C materials by their very nature flow more easily than

Amorphous materials.
The same mechanism that allows the material to fold up
into dense crystals allows the polymer chains to slide past
one another easily in the melted state.
For this reason materials like Nylon
require very tight tolerances on their
tooling to prevent melted plastic from
leaking out of the cavities causing
flash.
Flash

Properties

Weather Resistance

When it comes to weather resistance, the most damaging

aspect of weathering is generally considered to be
Ultraviolet light.
The UV light breaks down the chains of the polymers
making them more brittle, causing colors to fade or
yellow, and causing additives in the polymers to migrate
to the surface (chalking).

Properties

Weather Resistance

Amorphous polymers have better chemical resistance to

weathering effects than S/C polymers.
The crystals in the S/C polymers diffract the light so the
UV rays spend more time within the polymer structure
and do more damage. The clear amorphous polymers
allow the damaging radiation to pass through doing less
damage.

Properties

Shrinkage

Because they fold up into crystal structures, S/C materials

have higher shrinkage rates when compared to
Amorphous materials.
In injection molding most amorphous materials will shrink
between 0.003-0.007 in/in (0.3-0.7%)
S/C materials shrink differently depending upon the level
of crystallinity that they achieve.
Some will shrink over 0.025 in/in depending on
processing variables,
part thickness, and additives.

Material Types
Amorphous
Polyvinyl Chloride (PVC)
General Purpose Polystyrene (GPPS)
Polycarbonate (PC)
Polymethylmethacrylate (PMMA or Acrylic)
Acrylonitrile Butadiene Styrene (ABS a terpolymer)

Material Types
Semi-crystalline
Polyethylene (PE, HDPE, LDPE, etc.)
Polypropylene (PP)
Polyamides (PA Nylon)
Polyesters
Polyethylene Terephthalate (PET)
Polybutylene Terephthalate (PBT)
Polyoxymethylene (POM - Acetal)
Polytetrafluoroethylene (PTFE Teflon)

Morphologies
Amorphous structure random,
unordered
ex.
Polystyrene
Crystalline structure regular, order
ex.
Polyethylene,
Polypropylene

Polymer Microstructure
Polyolefins with side chains have stereocenters on every other carbon
n

CH3

CH3 CH3 CH3 CH3 CH3 CH3 CH3

With so many stereocenters, the stereochemistry can be complex.

There are three main stereochemical classifications for polymers.
Atactic: random orientation
Isotactic: All stereocenters have same orientation

Syndiotactic: Alternating stereochemistry

153

Capable of crystallizing

Why is this important?

Tacticity affects the physical properties

Atactic polymers will generally be amorphous, soft,

flexible materials
Isotactic and syndiotactic polymers will be more
crystalline, thus harder and less flexible

Polypropylene (PP) is a good example

Atactic PP is a low melting, gooey material

Isoatactic PP is high melting (176), crystalline, tough
material that is industrially useful
Syndiotactic PP has similar properties, but is very
clear. It is harder to synthesize

155

Polymer Crystallinity
Polymers are rarely 100%
crystalline
Difficult for all regions
of all chains
crystalline
to become aligned region
Degree of crystallinity

expressed as % crystallinity.
-- Some physical properties
depend on % crystallinity.
-- Heat treating causes
crystalline regions to grow
and % crystallinity to
increase.

amorphous
region

156

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.

The effect of temperature on the structure and

behavior of thermoplastics.

Thermoplastics
The crystalline phases of such polymers are
characterized by their melting temperature
(Tm).
Many thermoplastics are completely amorphous
and incapable of crystallization, these amorphous
polymers (and amorphous phases of
semicrystalline polymers) are characterized by
their glass transition temperature (Tg).
the temperature at which they transform abruptly
from the glassy state (hard) to the rubbery state
(soft).

Thermoplastics
Glass transition temperature (Tg)
This transition corresponds to the
onset of chain motion
below the Tg the polymer chains are
unable to move and are frozen in
position.

Both Tg and Tm increase with increasing

chain stiffness and increasing forces of
intermolecular attraction

Thermosets
Thermosets - normally rigid materials network polymers in which chain motion
is greatly restricted by a high degree of
crosslinking
As with elastomers, they are intractable
once formed and degrade rather than
melt upon the application of heat.

Elastomers
Elastomers - crosslinked rubbery
polymers - rubber networks - that can be
easily stretched to high extensions (3x to
10x original dimensions)
the rubbery polymer chains become
extended upon deformation but are
prevented from permanent flow by
crosslinking, and driven by entropy, spring
back to their original positions on removal
of the stress.

Polysaccharides
The size of polysaccharide molecules can vary,
occurring as polydispersed molecules that have
a range of 100 to 100,000 monosaccharide
units
MW 16,000 - 16,000,000 daltons

There are a number of methods used to

determine the molecular weight of
polysaccharides
viscosity*, light scattering, ultracentrifugation,
osmometry and titration are most common
(*viscosity is routinely used, but is not an absolute method and
can be used only in conjunction with one of the other methods)

Molecular Weight
Distribution

The simplest, most common molecular

weight is the number-average
molecular weight (n)
end-group analysis or colligative
properties (b.p. elevation, osmotic
pressure, etc)

others commonly used are weightaverage molecular weight (w), zaverage molecular weight (z) and
viscosity-average molecular weight
( )

Number-average molecular
weight (n)
based on methods of counting the
number of molecules in a given weight of
polymer
totalweight of a polymer sample, w, is
the
N = number of molecules
w the wsum
= each
molecular
weight
molecular
i ofNthe
i M i weightsMof
i 1
ipresent
1
species

Mn

N
i 1

M N
i 1

N
i 1

Weight-average molecular
weight (w)
determination of molecular weight
based on size rather than the number
of molecules
the greater the mass, the greater the

contribution
tothe measurement
2
w = weight fraction
wi M i N i M i

M = molecular weight
i 1
i 1
Mw

N = number of molecules
wi N i M i
i 1

i 1

Z-average molecular weight

(z)
some molecular weight determination
methods (e.g. sedimentation
equilibrium) yield higher molecular
weight averages - z

Mz

3
N
M
i i
i 1

2
N
M
i i
i 1

wi M i

i 1

w M
i 1

w = weight fraction
M = molecular weight
N = number of molecules

Number-average molecular weight

(n)
Example
- a polymer sample consists of 9
molecules of mw 30,000 and 5 molecules of

mw 50,000
M i Ni

(9 30,000) (5 50,000)
i 1
Mn

37,000
(9 5)
Ni
i 1

Weight-average molecular weight

(w) the previous example - 9 molecules of
Consider
molecular weight 30,000 and 5 molecules of
molecular weight 50,000

9(30,000) 5(50,000)
Mw
40,000
9(30,000) 5(50,000)
2

Z-average molecular weight (z)

Consider the previous example - 9 molecules of
molecular weight 30,000 and 5 molecules of
molecular weight 50,000

9(30,000) 5(50,000)
Mz
42,136
2
2
9(30,000) 5(50,000)
3

A Typical Molecular Weight

Distribution Curve
104 wi

4.0

n = 100 000 g mol-1

w = 199 900 g mol-1

3.0

2.0

z = 299 850 g mol-1

1.0

200 000

400 000

600 000

800 000

1 000 000

Mi (g mol-1)

Molecular Weight of Polymers

Unlike small molecules, polymers are typically a mixture of differently

sized molecules. Only an average molecular weight can be defined.

Viscosity average M.W. (Mv):

Average determined by viscosity
measurements. Closer to Mw than
Mn

Mv Mn
Mw

#
o
f
m
o
le
cu
le
s

Measuring molecular weight

Size exclusion chromatography
Viscosity
Measurements of average molecular
weight (M.W.)
Number average M.W. (Mn): Total
weight of all chains divided by # of
chains
Weight average M.W. (Mw):
Weighted average. Always larger
than Mn

increasing molecular weight

171

What the Weights Mean

Mn: This gives you the true average weight
Let's say you had the following polymer sample:
2 chains: 1,000,000 Dalton 2,000,000
5 chains: 700,000 Dalton
3,500,000
10 chains: 400,000 Dalton 4,000,000
4 chains: 100,000 Dalton
400,000
2 chains: 50,000 Dalton
100,000
10,000,000
10,000,000/23 = 435,000 Dalton
1 Dalton = 1 g/mole

172

Weight Average Molecular Weight

Mw: Since most of the polymer mass is in the heavier fractions, this
gives the average molecular weight of the most abundant polymer
fraction by mass.
2,000,000
0.20 1,000,000 200,000
10,000,000
3,500,000
0.35 700,000 245,000
10,000,000
4,000,000
0.40 400,000 160,000
10,000,000
400,000
0.04 100,000 4,000
10,000,000
100,000
0.01 50,000 500
10,000,000
Total 609,500
173

Polymer Solution Viscosity

When a polymer is dissolved in a
solvent and then subjected to flow
through a narrow capillary it exerts a
resistance to that flow. This resistance
is very informative.
It provides information on the size of
the polymer
Its Flexibility and shape in solution
Its interactions with the solvent it is

Polymer Melts
To shape a thermoplastic polymer it
must be heated so that it softens to
the consistency of a liquid
In this form, it is called a polymer
melt
Important properties:
Viscosity
Viscoelasticity

Viscosity of a polymer melt decreases with temperature,

thus the fluid becomes thinner at higher temperatures

Figure 13.2
Viscosity as a
function of
temperature for
selected polymers
at a shear rate of
103 s-1

Viscoelasticity
Combination of viscosity and elasticity
Possessed by both polymer solids
and polymer melts
Example: die swell in extrusion, in
which the hot plastic expands when
exiting the die opening

Various Fillers