Chapter 1 - Introduction To Polymers

NE 333
Polymer Properties and

Polymerization
1
NE 333 Polymer Properties and Polymerization
Course offered in Spring.
Contents The course starts with an introduction to the type of polymers found in our day-to-day
life. Mechanical and solution properties will be introduced.
Polymer characterization techniques are followed, such as gel permeation
chromatography, light scattering, viscosity, and osmometry.
The most frequently encountered types of polymerization (condensation, radical, and
ionic polymerizations) are described briefly.
The rest of the course focuses on polymer syntheses yielding polymeric structures in the
nanoscale. To this end, emulsion polymerization and supramolecular chemistry will be
introduced.
Textbooks Principles of Polymerization (3rd Edition) by G. Odian (Wiley: NY, 1991; QD281.P603
1991), Polymers: Chemistry and Physics of Modern Materials (2nd Edition) by J. M. G.
Cowie (Blackie Academic: Glasgow, 1991; QD381.C68x 1991), Elements of Polymer
Science and Engineering by A. Rudin (Academic Press: San Diego, 1999; QD381.R8
1999).
Professor Dr. Xiaosong Wang; Room: QNC-3169; E-mail: xiaosong.wang@uwaterloo.ca
Office hours: Mondays 11:30 12:30
Teaching Assistants Mr. Nimer Murshid, Room: QNC-3614, Tel: 37986, e-mail: nmurshid@uwaterloo.ca;
Office hours: Tuesdays 11:30 12:30
Mr. Aklilu Worku, Room: C2-166, Tel: 35245, e-mail: aworku@uwaterloo.ca;
Office hours: Wednesdays 11:30 12:30
Evaluation Two assignments (20%), mid-term exam (20%), and a 21/2-hour final exam (60%).
2
3
Who is Xiaosong Wang?
Education
B. Sc.: Chemistry (China)
Ph. D.: Polymer Science and Materials(China)
Experience
Post-Doc #1: U. of Sussex (UK)
Post-Doc #2: U. of Toronto (Canada)
2006 2011: University of Leeds
2011 present: University of Waterloo
Expertise
Supramolecular chemistry; Functional polymers;
Nanomaterials
Introduction
Chapter Overview
Natural polymers and the establishment of
polymer science
Examples of synthetic polymers
Polymer size and its importance
Polymer thermal and mechanical properties
Terminology/nomenclature
5
DNA
DNA, or deoxyribonucleic acid, is the
hereditary material in humans and almost all
other organisms.
The information in DNA is stored as a code made

up of four chemical bases: adenine (A), guanine
(G), cytosine (C), and thymine (T). DNA bases pair
up with each other, A with T and C with G, to form
units called base pairs. Each base is also attached
to a sugar molecule and a phosphate molecule.
Together, a base, sugar, and phosphate are called
a nucleotide. Nucleotides are arranged in two long
strands that form a spiral called a double helix.
Large molecules, repeat units, covalent and noncovalent bonds, structure

conformations, solid and solution properties, material functions,
6
Protein
7
Protein and protein misfolding
8
9
Cellulose and Starch:
Polysaccharides
10
Cellulose and Starch
(glucose)
In starch, all the glucose repeat units are oriented in the
same direction. But in cellulose, each succesive
glucose unit is rotated 180 degrees around the axis of
the polymer backbone chain, relative to the last repeat
unit.
Molecular weights:
Glucose: 180 g.mol-1
Cellulose: 350,000 g.mol-1 3,000,000 g.mol-1
Amylose: 90,000 g.mol-1 4,000,000 g.mol-1
11
Polymer Materials and Science
Natural rubber is an elastic hydrocarbon
polymer that was originally derived from latex, a
milky colloid found in the sap of Hevea trees.
The purified form of natural rubber is the chemical

polyisoprene, which can also be produced
synthetically.
Vulcanization
The vulcanized material is less sticky and has superior

mechanical properties. A vast array of products are made with
vulcanized rubber including tires, shoe soles, hoses, and
hockey pucks. 12
Bakelite
Synthetic polymers. E.g.

Leo bakelands Bakelite
phenol-
formaldehyde(1907),
methyl rubber
13
Demonstrating that Polymers are Macromolecules
Starch Natural rubber
Elemental analysis Elemental analysis
C5H8
C6H10O5 (1913) (Faraday in 1826)
Glucose Starch is a large Isoprene Rubber is a large

aggregate of glucose-like aggregate of rubber-like
molecules! (1913) molecules! (1905)
14
Chemical structure of rubber proposed by Harries in 1905.
CH3
H2C CH C CH2
H2C CH C CH2
CH3 x
15
Colligative Properties
Techniques that probe the They depend on the
nature/composition of molecules concentration of molecules and
molecular weights, not their
composition.
Elemental analysis
Osmotic pressure
Nuclear magnetic resonance
Boiling point elevation
Infra Red spectroscopy
Freezing point depression
Chemical composition Molecular weight of molecules size

(# of C, O, N, H atoms) (end of 19th century)
16
26
17
In 1920, Herman Staudinger wrote a paper

where he refuted the cyclic formulae of
polymers and proposed that polymers are
long chain molecules.
Cyclic isoprene
CH3
H2C CH C CH2
H2C CH C CH2
CH3 x
Herman Staudinger
Long chain molecule
18
This proposal for macromolecules was fiercely fought but
gained ground after 1930.
Letter to Hermann Staudinger (dated end 1920s)
"Dear collegue,
let me advise you to dismiss the idea of large
molecules, there are no organic molecules with a
molecular mass over 5,000 g/mol. Purify your
products, like for instance rubber, and they will
crystallize and reveal themselves as low molecular
weight substances."
19
Hermann Staudinger (1881 - 1965) (1953 Nobel
Prize)
introduction of the term "macromolecules" in
1922
Polymers are not aggregates of small
molecules held together by undefined forces.
Instead, they are macromolecules held
together by ordinary covalent bonds.
20
Rubber:
polyisoprene
cis-form (natural rubber)
21
Rubber: Polybutadiene
Polybutadiene is a synthetic rubber that is a polymer formed from the

polymerization process of the monomer 1,3-butadiene. Polybutadiene has a
high resistance to wear and is used especially in the manufacture of tires,
which consumes about 70% of the production.
22
Thermoplastic SBS Rubber
23
Plastics: polyethylene
Polyethylene is the most popular plastic in the world.

This is the polymer that makes grocery bags, shampoo bottles, children's toys, and
even bullet proof vests!
A molecule of polyethylene is nothing more than a long chain of carbon atoms,
with two hydrogen atoms attached to each carbon atom.
24
Plastics: polypropylene
Polypropylene is a very useful polymer. It serves double duty, both as a plastic and as a fiber. As
a plastic it is used to make things like dishwasher-safe food containers, because unlike the more
common polyethylene plastic, it melts at a higher temperature so it won't bend or warp in the
dishwasher.
As a fiber, polypropylene is used to make indoor-outdoor carpeting, the kind that you always
find around swimming pools and miniature golf courses. It works well for outdoor carpet
because it is easy to make colored polypropylene, and because polypropylene doesn't absorb
water, like nylon does.
25
Plastics: Poly(vinyl chloride)
PVC is useful because it resists two things that hate each other: fire and water. Because of it's water
resistance it is used to make raincoats and shower curtains and water pipes.
It has flame resistance, too, because it contains chlorine. When you try to burn PVC, chlorine atoms
are released, and chlorine atoms inhibit combustion.
The "vinyl" siding used on houses is made of poly(vinyl chloride). Inside the house, PVC is used to
make linoleum for the floor.
26
Plastics: polystyrene
polystyrene is clear, hard, and rather brittle. It is an inexpensive resin per unit weight. It
is a rather poor barrier to oxygen and water vapor and has a relatively low melting point.
Polystyrene is one of the most widely used plastics, the scale of its production being
several billion kilograms per year. Polystyrene can be naturally transparent, but can be
colored with colorants. Uses include protective packaging (such as packing peanuts and
CD and DVD cases), containers (such as "clamshells"), lids, bottles, trays, tumblers, and
disposable cutlery.
27
Atactic polystyrene
The only commercially important form of polystyrene is atactic, in
which the phenyl groups are randomly distributed on both sides of the
polymer chain. This random positioning prevents the chains from
aligning with sufficient regularity to achieve any crystallinity. The
plastic has a glass transition temperature Tg of ~90 C. Polymerization
is initiated with free radicals
Syndiotactic polystyrene
Ziegler-Natta polymerization can produce an ordered syndiotactic
polystyrene with the phenyl groups positioned on alternating sides of the
hydrocarbon backbone. This form is highly crystalline with a Tm of
270 C (518 F).
28
Plastics: PMMA
PMMA is more transparent than glass. When glass windows are made too thick,
they become difficult to see through. But PMMA windows can be made as much
as 13 inches (33 cm) thick, and they're still perfectly transparent. This makes
PMMA a wonderful material for making large aquariums, with windows which
must be thick in order to contain the high pressure of millions of gallons of
water.
29
Fibres: polyacrylonitrile
Polyacrylonitrile is usually used to make other polymers like, carbon fiber.
Fibers of polyacrylonitrile have been uses in hot gas filtration systems, outdoor
awnings, sails for yachts, and even fiber reinforced concrete. But mostly
copolymers containing polyacrylonitrile are used as fibers to make knitted
clothing, like socks and sweaters, as well as outdoor products like tents. If the
label of some piece of clothing says "acrylic", then it's made out of some
copolymer of polyacrylonitrile, like acrylonitrile and methyl methacrylate.
30
ABS Plastics
ABS is very strong and lightweight. It is strong enough to be used to make automobile
body parts.
ABS is a stronger plastic than polystyrene because of the nitrile groups of its
acrylonitrile units. The nitrile groups are very polar, so they are attracted to each
other.
This strong attraction holds ABS chains together tightly, making the material
stronger. Also the rubbery polybutadiene makes ABS tougher than polystyrene.
31
Polyester
Polyester is a category of polymers that contain the ester functional group

in their main chain.
32
Polyamide: Nylon
A polyamide is a macromolecule with repeating units linked by amide bonds.

Polyamides occur both naturally and artificially. Examples of naturally
occurring polyamides are proteins, such as wool and silk.
33
Terminology
Monomer = styrene
n < 20 Oligomer
n > 20 Polymer
Monomer units
Structural units = building block
Repeating units = shortest repeating sequence
34
Terminology
Polystyrene Structural Unit = Repeating Unit
H2C
n CH
Poly(vinyl alcohol) Structural Unit = Repeating Unit
CH2 CH CH2 CH
n
OH OH
35
Terminology
Polymer: O O
poly(ethylene terephthalate) PET H OCH2CH2O C C OH

n
O O
Monomers HO CH2 CH2 OH HO C C OH
Ethylene glycol Terephthalic acid

O O
Repeating unit: OCH2CH2O C C
O O
Structural units OCH2CH2O C C
36
Terminology
backbone
X CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH Y
pendant groups
end groups
37
Terminology
Degree of polymerization
x = Number of structural units/chains
Poly(vinyl chloride)
X CH2 CH Y x = 100
Cl 100
Poly(ethylene terephthalate)
O O
H OCH2CH2O C C OH x = 2 100 = 200
100
O O
OCH2CH2O C C 38
Terminology
Molecular weight
M = x Mo + M(end groups) Mo = average molecular
weight of the structural unit
X CH2 CH Y CH2 CH M = 100 62.5 + M(e.g.)

Cl 100 Cl
Structural unit
(Mo = 62.5 g.mol-1)
O O
H OCH2CH2O C C OH M = 200 96 + M(e.g.)
100
O O
OCH2CH2O C C
Mo = (60 + 132)/2 = 96 g.mol-1

(60 g.mol-1) (132 g.mol-1) 39
Official method: Terminology
O O
H OCH2CH2O C C OH M = 200 96 + M(e.g.)
100
O O
OCH2CH2O C C
Mo = (60 + 132)/2 = 96 g.mol-1

(60 g.mol-1) (132 g.mol-1)
Unofficial method:
M = 100 60 + 100 132 + M(e.g.) = 200 96 + M(e.g.)
Ethylene glycol Terephthalic acid
(62 g.mol-1) (166 g.mol-1)

40
Terminology
The functionality f of monomer is the number of bonds formed in the

reaction. It may depend on the polymerization reaction conditions.
O H O
n H2N R C OH H N R C OH + (n-1) H2O
n
amine acid polyamide
The functionality f = 2.
41
Terminology
The functionality f of monomer depends on the polymerization reaction.
H2C CH
H2C CH
H2C CH n
n
n
H2C CH n
42
f=2 f=4 f=2
Terminology
Structure
Linear chain
Branched
Comb
Ladder (DNA)
Network
Dendritic (tree-like)
43
Polymerization Reactions
Condensation polymerization
O O
n HO CH2 CH2 OH + n H3CO C C OCH3
O O
H OCH2CH2O C C OH + (2n-1) CH3OH
n
Small molecule elimination, functional groups in the backbone
Addition polymerization
n CH2 CH2 CH2 CH2 n
No elimination of small molecules
opening of double bonds C C backbone
44
Exceptions
Polyurethanes
(diol) (di-isocyanate)
n HO-R1-OH + n O C N R2 N C O
(polyurethane)
O H H O
O R1 O C N R2 N C
n
Condensation polymerization with no
elimination of small molecule.
Polyoxides
O Addition polymerization
n CH2 CH2 CH2 CH2 O with oxygen atoms in the
n
backbone.
45
Copolymers
Copolymers are made of at least two different repeating units.
Random: -A-A-B-A-A-B-B-A-B-A-B-B-B-A-B-A-A-
Alternating: -A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-
Block: -A-A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-
Graft: -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-
| |
B B
| |
B B
| |
B B
| |
B B
| |
B B
| |
B B 46
Copolymers
Copolymers are made of at least two different repeating units.
Random: -A-A-B-A-A-B-B-A-B-A-B-B-B-A-B-A-A-
Alternating: -A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-B-A-
Block: -A-A-A-A-A-A-A-A-A-B-B-B-B-B-B-B-B-
Graft: -A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-A-
| |
B B
| |
B B
| |
B B
| |
B B
| |
B B
| |
B B 47
Copolymers
Examples:
Homopolymer: poly(vinyl chloride) PVC
CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH
Cl Cl Cl Cl Cl Cl Cl
(semicrystalline polymer)
Random copolymer: Poly(vinyl chloride-co-vinyl acetate)
CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH
Cl OAc Cl OAc OAc Cl Cl
(less crystalline, more flexible, and optically clearer polymer)
Alternating copolymer: Poly(styrene-alt-maleic anhydride)
CH2 CH CH CH CH2 CH CH CH CH2 CH CH CH
O O O O O O O O O
(polymeric surfactant)
48
Copolymers
Poly(ethylene terephthalate) (PET) is a condensation homopolymer.

O O
HO CH2 CH2 O C C O CH3
n
(same repeating unit)
Poly(ethylene terephathlate-co-butylene terephthalate) is a copolymer.
O O O O
C4H8 O C C O CH2 CH2 O C C O
p n
repeating unit #1 repeating unit #2
49
Nomenclature
Non-systematic names are mostly used.

Systematic names from IUPAC:
Styrene (mostly used)

Ethenylbenzene (in chemical abstract)
Vinylbenzene (in older chemical abstract)
Phenylethylene (IUPAC)
50
Polymer Molecular Weight
MW2
Mechanical Sterngth MW1
MWo Polymer Molecular Weight

MW < MWo 1,000 g.mol-1 : The polymer has no mechanical strength.
The chance is that it is a liquid.
MWo < MW < MW1 5,000 10,000 g.mol-1 : The polymer develops
mechanical strength. At MW1, polymer entanglements begin to form.
MW1 < MW < MW2 : Mechanical strength improves as more
entanglements are generated.
MW2 < MW : A sufficient number of entanglements has been formed 51
and a further increase in MW no longer affects the mechanical strength.
Three things make polymer different with small molecules
1) Summation of intermolecular forces

2) Chain entanglement
4) Time scale of motion
52
intermolecular forces affect polymers just like small molecules. But with
polymers, these forces are greatly compounded. The bigger the molecule, the
more molecule there is to exert an intermolecular force. Even when only weak
Van der Waals forces are at play, they can be very strong in binding different
polymer chains together. This is one reason why polymers can be very strong as
materials.
Polyethylene, for example is very nonpolar. It only has Van der Waals forces to
play with, but it is so strong it's used to make bullet proof vests.
CH4 Wax: CnHn+2 (n < 100) Polyethylene (C2H4)n
53
Amorphous crystalline polymers
Thermoplastic, thermoset; elastomer, fiber
Entangled polymers are characterized with effective internal

scale, commonly known as the length of macromolecule between
adjacent entanglements Me.
54
Reptation
To relax, the polymeric

material must wait a period
Entanglements with other polymer chains restrict trep for the chain to move
polymer chain motion to a thin virtual tube passing
through the restrictions. Without breaking polymer out of its tube.
chains to allow the restricted chain to pass through it,
the chain must be pulled or flow through the
restrictions. The mechanism for movement of the trep depends of the
chain through these restrictions is called reptation. chain size 55
Reptation theory describes the effect of polymer chain
entanglements on the relationship between molecular mass and
chain relaxation time (or similarly, the polymers zero-shear
viscosity). The theory predicts that, in entangled systems, the
relaxation time is proportional to the cube of molecular mass,
M: ~ M3. This is a reasonable approximation of the actual
observed relationship, ~ M3.4.
56
Effect of Polymer Concentration
individual
overlap
polymer coils entanglements
concentration
57
58
Polymer Characterization
Molecular Mass: GPC, SLS, end group analysis, etc.

Molecular Structure: ultraviolet-visible spectroscopy,
infrared spectroscopy, Raman spectroscopy, nuclear
magnetic resonance spectroscopy, electron spin resonance
spectroscopy, and mass spectrometry
Morphology: TEM, WAXS, SAXS
Thermal properties: Tg, Tc, Tm
Mechanical and viscoelastic properties
59
Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
technique used to determine Tg and Tm for polymers.
heater heater
The DSC is heated at a constant rate (10 oC/min is

typical). The computer controls the temperature in
both sample holders by adjusting the amount of heat
flowing through the heater. Difference in the heat
flows going through both heaters indicates that the 60
sample is going through a transition.
Glass Transition
Heat flow
semi-crystalline
melt material melt
glass
Tg Tc
Tm
Temperature
Heat flow from DSC to sample

61
Glass Transition
Tg: At Tg, local motion of the chains is enabled. For local

motion of the chains to be enabled, heat must be provided to
the sample (heat flows from DSC to sample: positive heat
flow). heater heater
Tc: When heated above Tg, the chains experience enough
freedom so that some of their parts can arrange themselves
into microcrystals. Crystallization releases heat. Heat flows
from sample to DSC: negative heat flow.
Tm: As the temperature increases further, the melting
Heat flow
temperature (Tm) is reached and the microcrystals melt. For
this to happen, the sample needs to absorb heat and heat flows
from DSC to sample: positive heat flow.
Transitions observed by DSC occur over a range of Tg Tc Tm

temperatures.
Temperature
62
Glass Transition

Heat flow

temperatures.
Temperature
63
Glass Transition

Heat flow

temperatures.
Temperature
64
Glass Transition

Heat flow

temperatures.
Temperature
65
Glass Transition
How would the DSC plot of a sample of atactic polystyrene look like?
Heat flow
semi-crystalline
melt material melt
glass atactic
Tg Tc polystyrene
Tm
Temperature
66
Glass Transition
In a DSC experiment, the temperature is changed at a known rate (l =
dT/dt). The heat flow (HF = dq/dt) is monitored. Taking the ratio HF / l
yields dq / dT.
1st law of thermodynamics: dH = dq + VdP
Since the experiment is conducted at constant pressure, dP = 0 and
dH = dq CpdT
Putting it all together, one finds that Cp = dq / dT = HF / l
Heat flow
semi-crystalline
melt material melt
glass
Tg Tc
Tm
67
Temperature
Glass Transition
Intramolecular parameters
The glass transition indicates the onset of segmental motions. Segmental motions can be
visualized with the crankshaft mechanism which allows sections of the chain to relax without
involving large scale motions of the entire chain found in the viscous region of the stress-strain
curve.
The crankshaft mechanism is enabled by rotation of the backbone bonds about one another. The
substituents on the backbone chain atoms hinder rotation around the backbone bonds due to steric
hindrance and constitute a barrier to internal rotation.
cis gauche skewed trans gauche skewed cis
vinyl polymer
` ` ` ` ` `
Potential Barrier
68
Glass Transition
The glass transition temperature (Tg) is the most important single
parameter that determines what a given amorphous polymer will
be used for.
Polymers structure Tg (oC)

Polydimethylsiloxane -O-Si(CH3)2- -127
Polyethylene -CH2-CH2- -125
Polyisoprene -CH2-C(CH3)=CH-CH2- -73
Polyisobutylene -CH2-C(CH3)2- -73
Poly(ethylene terephthalate) -O-CH2-CH2-O-CO-C6H4- +61
CO-
Poly(vinyl chloride) -CH2-CHCl- +81
Polystyrene -CH2-CH(C6H5)- +100
Poly(methyl methacrylate) -CH2-C(CH3)(CO2CH3)- +105
69
Glass Transition
Question: Which polymer would you use to make a window?

CO-
70
Glass Transition

CO-
71
Glass Transition

CO-
72
Glass Transition
Question: Which polymer would you use to make a rubber band?

CO-
73
Glass Transition

CO-
74
Glass Transition

CO-
75
Glass Transition
Polyethylene is an interesting case. Its Tg equals -125 oC, yet PE is
sufficiently rigid to be used extensively for packaging applications.

CO-
76
Glass Transition
Polyethylene is an interesting case. Its Tg equals -125 oC, yet PE is sufficiently rigid to
be used extensively for packaging applications. The rigidity of PE is due to PE
microcrystals which bind the chain together and inhibit flow. Tm for PE equals
+120 oC.
Defects which hinder crystallization lower the rigidity of PE. Thus high density
polyethylene (HDPE) is more rigid than low density polyethylene (LDPE).
DSC trace for polyethylene

Cp = Heat flow / l
semi-crystalline
melt material melt
glass
Tg = -125 oC
Tc Tm = +120 oC
Temperature 77
Mechanical properties
Ultimate tensile strength (UTS),

often shortened to tensile strength
(TS) or ultimate strength, is the
capacity of a material or structure
to withstand loads tending to
elongate
The tensile test measures the

resistance of a material to a static or
slowly applied force. The data
obtained from the tensile tests
describes many mechanical features
of the polymer.
78
Stressstrain relationship
thermoplastic polymer
79
Amorphous polymers
there is a drop in stress beyond the yield

point. This is because the initially tangled
and intertwined chains become straight and
untangled. Once the chains are straighten,
additional stress causes necking, in which
there is the continued sliding and
deformation of the chains
80
Semi-crystalline polymers
It is only different from an amorphous stress-strain curve

because it lacks the drawing region.
81
82
Definition Description
Yield Point (strength): Yield point is the first point (load) at
which the specimen yields. This is when the specimen's cross-
sectional area begins to decrease. This is called necking.
Modulus of Elasticity: The ratio of stress to strain within the

elastic region of the stress-strain curve.
Yield Elongation: The strain at the yield point.
Elastic Region: The portion of the curve before the yield point.
Plastic Region: The portion of the curve after the yield point
Ultimate (tensile )strength: the maximum stress a material can

withstand before failing.
83
Ultimate elongation: The total elongation just before fracture
Viscoelastic properties of polymers
How do materials behave when deformed ?
Elastic (Energy Stored) Viscous (Energy Dissipated)
Viscoelastic
i.e. Polymers
85
The principal method of measuring the material properties of a system is with
a transducer. A transducer measures the force of the system in response to a
perturbation by the motor, which applied either a known stress and measured
the resultant strain, or vice-versa.
the stress is equal to the force per unit area, it is clear that increasing the area
of the fixture will increase the force experienced by the transducer.
For systems with extremely low viscosities, the surface area is maximized, as
can be seen with the concentric cylinder set-up. As the viscosity increases, the
area requirement is decreased, with several different size fixtures for cone and
plate and parallel plate available based on the system requirements.
86
Dynamic Oscillatory Measurements
Strain Stress
Strain Controlled Elastic
Rheometer
=0
Top Plate
Viscoelastic
Sample 0 < < 90
Bottom Plate Viscous
= 90
Phase angle or Tan Delta (the tangent of the phase angle) is related to, and is
an indicator of magnitudes of elasticity.
88
The rheological behaviour of polymeric systems
is profoundly influenced by their molecular
weights and molecular weight distributions.
This information can be derived from the cross-

over points for G and G
Zero-shear viscosity and the relationship

between viscosity and frequency.
89
90
Making isothermal measurements over a range of frequencies can give a
valuable insight into a polymers' structure through the study of the resultant
rheological responses.
Data of most interest derived from a frequency sweep are Complex Viscosity
(h*), Storage and Loss modulus (G' & G"), and Phase angle ().
The point at which the G' & G" curves cross over is an excellent indicator of
magnitudes of average molecular weight and molecular weight distribution
when comparing samples - the lower down the frequency range the curves
cross, the higher the average molecular weight and the position of the cross-
over on the modulus axis gives an indication of molecular weight distribution
(increased modulus = narrower Molecular weight distribution).
91
the plot gives a virtually linear response across the nine grades
which represented the range of Mw commercially available -
thus giving a useful 'look up' chart to compare future HDPE
rheological measurements against to provide an indication of
magnitude of Mw. 92
The viscosity plateau at a higher frequency suggests narrower PDI93
The higher zero shear viscosity, the larger molecular weight
Summary
Polymer classifications.
Chemical structures for the synthetic polymers.
Terminology for polymer science.
What make polymer special?
Polymers thermal properties. (DSC, Tg, Tc, Tm)
Mechanical properties. (tensile behaviour)
Viscoelastic properties. (G, G, Tan delta)
94

Chapter 1 - Introduction To Polymers

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NE 333

Polymer Properties and

The information in DNA is stored as a code made

Large molecules, repeat units, covalent and noncovalent bonds, structure

The purified form of natural rubber is the chemical

The vulcanized material is less sticky and has superior

Synthetic polymers. E.g.

Starch Natural rubber

Elemental analysis Elemental analysis

Glucose Starch is a large Isoprene Rubber is a large

Chemical structure of rubber proposed by Harries in 1905.

Chemical composition Molecular weight of molecules size

In 1920, Herman Staudinger wrote a paper

Long chain molecule

cis-form (natural rubber)

Polybutadiene is a synthetic rubber that is a polymer formed from the

Polyethylene is the most popular plastic in the world.

Polyester is a category of polymers that contain the ester functional group

A polyamide is a macromolecule with repeating units linked by amide bonds.

Polystyrene Structural Unit = Repeating Unit

Poly(vinyl alcohol) Structural Unit = Repeating Unit

poly(ethylene terephthalate) PET H OCH2CH2O C C OH

Ethylene glycol Terephthalic acid

X CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH Y

X CH2 CH Y CH2 CH M = 100 62.5 + M(e.g.)

Mo = (60 + 132)/2 = 96 g.mol-1

Mo = (60 + 132)/2 = 96 g.mol-1

Ethylene glycol Terephthalic acid

(62 g.mol-1) (166 g.mol-1)

The functionality f of monomer is the number of bonds formed in the

The functionality f of monomer depends on the polymerization reaction.

Copolymers are made of at least two different repeating units.

Copolymers are made of at least two different repeating units.

Poly(ethylene terephthalate) (PET) is a condensation homopolymer.

Poly(ethylene terephathlate-co-butylene terephthalate) is a copolymer.

Non-systematic names are mostly used.

Styrene (mostly used)

Mechanical Sterngth MW1

MWo Polymer Molecular Weight

1) Summation of intermolecular forces

CH4 Wax: CnHn+2 (n < 100) Polyethylene (C2H4)n

Thermoplastic, thermoset; elastomer, fiber

Entangled polymers are characterized with effective internal

To relax, the polymeric

Molecular Mass: GPC, SLS, end group analysis, etc.

Morphology: TEM, WAXS, SAXS

Thermal properties: Tg, Tc, Tm

Mechanical and viscoelastic properties

The DSC is heated at a constant rate (10 oC/min is

Heat flow from DSC to sample

Tg: At Tg, local motion of the chains is enabled. For local

Transitions observed by DSC occur over a range of Tg Tc Tm

Tg: At Tg, local motion of the chains is enabled. For local

Transitions observed by DSC occur over a range of Tg Tc Tm

Tg: At Tg, local motion of the chains is enabled. For local

Transitions observed by DSC occur over a range of Tg Tc Tm

Tg: At Tg, local motion of the chains is enabled. For local

Transitions observed by DSC occur over a range of Tg Tc Tm

Polymers structure Tg (oC)

Polymers structure Tg (oC)

Polymers structure Tg (oC)

Polymers structure Tg (oC)

Polymers structure Tg (oC)