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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/pro
perty 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 repeat repeat


unit unit unit
H H H H H H H H H H H H H H H H H H
C C C C C C C C C C C C C C C C C C
H H H H H H H Cl H Cl H Cl H CH3 H CH3 H CH3
Polyethylene (PE) Poly(vinyl chloride) (PVC) 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 Polymer
CH3
H3C
Polyethylene n
Ethylene Repeat unit

CH3
CH3 n
Polypropylene CH3 CH3 CH3 CH3 CH3 CH3 CH3
Propylene

CH3
Ph n
Polystyrene Ph Ph Ph Ph Ph Ph Ph
Styrene

CH3
Cl n
Poly(vinyl chloride) Cl Cl Cl Cl Cl Cl Cl
Vinyl Chloride
F2 F2 F2 F2 F2 F2
F2C CF2 C C C C C C CF3
F3C C C C C C C
F2 F2 F2 nF F2 F2
Tetrafluoroethylene Poly(tetrafluoroethylene): Teflon 2

16
17
18
Polyesters, Amides, and Urethanes
Monomer Polymer
O O
H2 H2
HO2C CO2H OH HO O C C O H
HO
Ethylene Poly(ethylene terephthalate n
Terephthalic
acid glycol Ester

O O O O
H
HO 4
OH H2N 4
NH2 HO N 4 N
4
Adipic Acid 1,6-Diaminohexane Nylon 6,6 H H n
Amide
O O
H H
HO2C CO2H H2N NH2 HO N N H
Kevlar n
Terephthalic 1,4-Diamino
acid benzene
H2
OCN C NCO OH
HO
Ethylene Spandex
4,4-diisocyantophenylmethane
glycol
O O
H H2 H H2 H2
HO N C N O C C O H Urethane linkage
n
19
Natural Polymers
Monomer Polymer

Isoprene Polyisoprene:
Natural rubber n
H OH H OH
HO H HO
HO O
HO OH HO OH
H OH Poly(ß-D-glycoside): H OH
H H cellulose H H n

ß-D-glucose
O O O O
H H
H3N H3N N N OH
O Polyamino acid:
protein R1 Rn+1 n Rn+2
R
Amino Acid
O O
DNA
O P O Base O P O
O Base
O O O
oligonucleic acid
OH DNA
O
Nucleotide DNA
Base = C, G, T, A 20
Rubbers

21
Polymer Classification
Polymers are commonly classified based on their
underlying molecular structure.

Polymers

Thermoplastics Elastomers Thermosets

Crystalline Amorphous
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 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).

27
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.
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 random
polymerized together
• random – A and B randomly
positioned along chain
• alternating – A and B alternate
in polymer chain alternating
• block – large blocks of A units
alternate with large blocks of B block
units
• graft – chains of B units grafted
onto A backbone

A– B–
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)-graft-
poly(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:
polyethylene, PVC, nylon.
46
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.
47
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 i 52
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 Monodisperse Paucidisperse

# # #

size 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 semi-
crystalline (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-co-
butadiene)
 Poly(ethylene), atactic Poly(propylene) and Poly(ethylene-co-
propylene)
 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 polymer’s
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: O
 poly(ethylene terephthalate) - Dacron C O

Polyamides: H O
 poly(caprolactam) - nylon 6 N C
Urethanes:
 carbamate linkages through reaction H O
of diisocyanates and diols. 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 C N

poly(butadiene-ran-acrylonitrile) poly(butadiene-alt-acrylonitrile)
Alternating Copolymers: Elastomers
Typical stress-strain curves at 0°C for unreinforced rubber vulcanizates:
1: poly(propylene-alt-butadiene) 2: natural rubber: cis-1,4-polyisoprene
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 nylon-
spandex
C: mechanical stretch
nylon
D: spandex
E: extruded latex

CHEE 890 J.S. Parent


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.

O O
O

ROOR
O
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

A
In* In A* A
Initiation
Addition Polymerization
Propagation

A
In* In A A* A
Initiation
Addition Polymerization
Propagation

A
In* In A A A* A
Initiation
Addition Polymerization

A nA
In* In A A A A* In A A A A A*
Initiation Propagation n

*A A A A A
A *A A A A A m
m

In A A A A A In A A A A A A A A A A
In A A A A A n
n n m

A* Combination
B A A A A
m
Chain Transfer Disproportionation
New reactive site
is produced
Termination
Reactive site is consumed
MW

k propagation
MW 
k ter mination

0 100
% conversion
Addition (Chain) Polymerization

– Initiation

– Propagation

– Termination

71
Types of Addition Polymerizations
Anionic

n Li+
Ph Li+ Ph
C4H9 C4H9
C3H7 Li n
Ph Ph Ph
Radical

n
Ph Ph
PhCO2• PhCO2 PhCO2
n
Ph Ph Ph
Cationic

n
Ph Ph
Cl3Al OH2 H H HOAlCl3
n
Ph Ph Ph
HOAlCl3
Step-Growth Polymerization

Stage 1
n n
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.

1000

1
Degree of Polymerization
Xn 
1 p
100


10

Xn = Degree of polymerization
p = mole fraction monomer 1
conversion 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole Fraction Conversion (p)
Nylon-6,6

O O O O
NaOH
Cl Cl H2N NH2 H
4 4 Cl 4
N 4 N
H H
Adipoyl chloride 1,6-Diaminohexane

O O
Adipoyl chloride H
in hexane HO N N
4 4
H H n
Nylon 6,6
6 carbon 6 carbon
diacid diamine
Diamine, NaOH, in H2O
Nylon-6,6
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 – Rubber
– Cotton – Wool
– Leather – 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
(>280°C) 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
–70°C.
• 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 mid-nineteenth century
when Charles Goodyear found that heating it with sulfur — a process
he called vulcanization — could greatly improve its properties.

cis-polyisoprene
Sifat-sifat Polimer
Specific Thermoplastic Properties
Thermoset data
Thermoset Properties
Mechanical properties of Polymers
Hooke’s 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 stress–strain 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;
ΔL 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 the tensile modulus or elastic modulus, is a


measure of the stiffness of an elastic material and is a quantity used to characterize
materials. It is defined as the ratio of the stress (force per unit area) along an axis to
the strain (ratio of deformation over initial length) along that axis in the range of
stress in which Hooke's law holds.
• 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


force F and 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 right-angles to
compressive or tensile stress
Strain

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


expressed as
ε = dl / lo
=σ/E
where
dl = change of length (m, in)
lo = initial length (m, in)
ε = unit less measure of engineering strain
E = Young's modulus (Modulus of Elasticity) (N/m2 (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 called linear, and are said to
obey Hooke's law. Examples of linear materials
include steel, carbon fiber, and glass. Rubber
and soil (except at very low strains) are non-
linear materials.
Modulus of Elasticity (Young's Modulus)
Slope of the stress-strain diagram within the elastic zone is called “Modulus of Elasticity”
or “Young’s 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 chemical structure.
Polymers require a Mechanical Property
particular MW, which
depends largely on the
chemical structure, to
have desirable
mechanical properties.
Molecular Weight
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

H
+ O + N
C R C R
- O - O
dipole-dipole H-bonding
H +
O N
+ C R R C
-
O -
O

A lower MW polyamide will produce good fiber


properties as compared to the polyester  H-
Polymer Morphology
• Hydrogen Bonding
– A dipole-dipole interaction for hydrogens bonded
to electronegative elements
• Electrostatic Interaction
R R

O O very important
H
H H
O
H
O
in cellulose
R R

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


Require short bond distance ~ 2.5Å (c-c ~ 1.46Å)
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 Amorphous
regions 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’
o Solid to Liquid
o Liquid to Gas
For thermoplastic materials, we are concerned with:
o Glass Transition Temperature
o Melting 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 – once it dips below the Tg
crystal formation stops
-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 Tg’s. 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 don’t 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 polymer’s
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 death.
Properties
Chemical Resistance
Plastic materials are used in virtually every aspect of today’s 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 don’t 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

CH3
n
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 (176º), 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 to
become aligned crystalline
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.
behavior of thermoplastics.
The effect of temperature on the structure and
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 weight-average
molecular weight (w), z-average molecular
weight (z) and viscosity-average molecular
weight (u)
– light scattering (w), sedimentation equilibrium
(z) and solution viscosity (u)
Number-average molecular weight (n)
– based on methods of counting the number of
molecules in a given weight of polymer
• the total weight of a polymer sample, w, is the sum of
the weights of each molecular species present

 
w   wi  N i M i
N = number of molecules
M = molecular weight
i 1 i 1

w M N i i
Mn  
 i 1

N
i 1
i N i 1
i
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
to the measurement

 

 wi M i  Ni M i
2
w = weight fraction
M = molecular weight
Mw  i 1

 i 1
 N = number of molecules

w i 1
i N M
i 1
i i
Z-average molecular weight (z)
some molecular weight determination methods
(e.g. sedimentation equilibrium) yield higher
molecular weight averages - z

 

 i i
N M 3
 wi M i 2
w = weight fraction
M = molecular weight
Mz  i 1

 i 1
 N = number of molecules

 i i
N M
i 1
2
w M
i 1
i i
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 N i i
(9  30,000)  (5  50,000)
Mn  i 1

  37,000
(9  5)
N i 1
i
Weight-average molecular weight (w)
Consider the previous example - 9 molecules of molecular
weight 30,000 and 5 molecules of molecular weight 50,000

9(30,000) 2  5(50,000) 2
Mw   40,000
9(30,000)  5(50,000)
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)3  5(50,000)3
Mz   42,136
9(30,000)  5(50,000)
2 2
A Typical Molecular Weight Distribution
Curve
104 wi

n = 100 000 g mol-1


4.0

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.
• Measuring molecular weight
• Size exclusion chromatography
• Viscosity
• Measurements of average molecular Mv Mn
weight (M.W.)
• Number average M.W. (Mn): Total Mw
weight of all chains divided by # of
chains
• Weight average M.W. (Mw):

m
Weighted average. Always larger
#
o
o
le
cu
le
s
f
than Mn
• Viscosity average M.W. (Mv): increasing molecular weight
Average determined by viscosity
measurements. Closer to Mw than
Mn 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 disolved
in.
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