Professional Documents
Culture Documents
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.
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
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.
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.
• Crosslinked: A continuous
network of polymer chains is
a crosslinked condition. In effect,
there is just one polymer chain
of infinite molecular weight.
A– B–
graft
43
Copolymers can be used to tailor functionality or generate
new phases and behaviors.
Graft copolymer,
example:
Poly(styrene)-graft-
poly(butadiene)
Molecular Structures for Polymers
secondary
bonding
secondary
bonding
Tetrahedral
arrangement
of C-H
Low M
high M
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.
# # #
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...
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
Polyamides: H O
poly(caprolactam) - nylon 6 N C
Urethanes:
carbamate linkages through reaction H O
of diisocyanates and diols. N C O
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).
O O
O
ROOR
O
O
O
Si(OMe)3
ROOR
Si(OMe)3
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
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
85
Cellulose
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.
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
O O very important
H
H H
O
H
O
in cellulose
R R
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
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.
CH3
n
CH3 CH3 CH3 CH3 CH3 CH3 CH3
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
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
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
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