NE 333

Polymer Properties and

Polymerization

NE 333

Polymer Properties and Polymerization

CourseofferedinSpring.

Contents

The course starts with an introduction to the type of polymers found in our day-to-day
life.Mechanicalandsolutionpropertieswillbeintroduced.
Polymer characterization techniques are followed, such as gel permeation
chromatography,lightscattering,viscosity,andosmometry.
The most frequently encountered types of polymerization (condensation, radical, and
ionicpolymerizations)aredescribedbriefly.
Therestofthecoursefocusesonpolymersynthesesyieldingpolymericstructuresinthe
nanoscale. To this end, emulsion polymerization and supramolecular chemistry will be
introduced.

Textbooks

PrinciplesofPolymerization(3rdEdition)byG.Odian(Wiley:NY,1991;QD281.P603
1991),Polymers:ChemistryandPhysicsofModernMaterials(2ndEdition)byJ.M.G.
Cowie(BlackieAcademic:Glasgow,1991;QD381.C68x1991),ElementsofPolymer
ScienceandEngineeringbyA.Rudin(AcademicPress:SanDiego,1999;QD381.R8
1999).

Professor

Dr.XiaosongWang;Room:QNC-3169;E-mail:xiaosong.wang@uwaterloo.ca
Officehours:Mondays11:3012:30
TeachingAssistants Mr.NimerMurshid,Room:QNC-3614,Tel:37986,e-mail:nmurshid@uwaterloo.ca;
Officehours:Tuesdays11:3012:30
Mr.AkliluWorku,Room:C2-166,Tel:35245,e-mail:aworku@uwaterloo.ca;
Officehours:Wednesdays11:3012:30
Evaluation
Twoassignments(20%),mid-termexam(20%),anda21/2-hourfinalexam(60%).
2

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
ChapterOverview
Naturalpolymersandtheestablishmentof
polymerscience
Examplesofsyntheticpolymers
Polymersizeanditsimportance
Polymerthermalandmechanicalproperties
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

Proteinandproteinmisfolding

CelluloseandStarch:
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.

Molecularweights:
Glucose:180g.mol
Cellulose:350,000g.mol3,000,000g.mol
Amylose:90,000g.mol4,000,000g.mol
11

Polymer Materials and Science

Natural rubberisanelastichydrocarbon
polymerthatwasoriginallyderivedfromlatex,a
milkycolloidfoundinthesapofHeveatrees.
Thepurifiedformofnaturalrubberisthechemical
polyisoprene,whichcanalsobeproduced
synthetically.
Vulcanization

Thevulcanizedmaterialislessstickyandhassuperior
mechanicalproperties.Avastarrayofproductsaremadewith
vulcanizedrubberincludingtires,shoesoles,hoses,and
hockeypucks.

12

Bakelite

Synthetic polymers. E.g.

Leo bakelands Bakelite
phenolformaldehyde(1907),
methyl rubber

13

Demonstrating that Polymers are Macromolecules

Starch
Elementalanalysis

C6H10O5(1913)

GlucoseStarchisalarge
aggregateofglucose-like
molecules!(1913)

Naturalrubber
Elementalanalysis
C5H8
(Faradayin1826)

IsopreneRubberisalarge
aggregateofrubber-like
molecules!(1905)
14

Demonstrating that Polymers are Macromolecules

ChemicalstructureofrubberproposedbyHarriesin1905.
CH3
H2C

CH

CH2

H2C

CH

CH2

CH3

15

Demonstrating that Polymers are Macromolecules

ColligativeProperties
Techniquesthatprobethe
nature/compositionofmolecules

Elementalanalysis
Nuclearmagneticresonance
InfraRedspectroscopy

Theydependonthe
concentrationofmoleculesand
molecularweights,nottheir
composition.
Osmoticpressure
Boilingpointelevation
Freezingpointdepression

Chemicalcomposition

Molecularweightofmoleculessize

(#ofC,O,N,Hatoms)

(endof19thcentury)

16

26

17

Demonstrating that Polymers are Macromolecules

In1920,HermanStaudingerwroteapaper
whereherefutedthecyclicformulaeof
polymersandproposedthatpolymersare
longchainmolecules.
Cyclicisoprene
CH3
H2C

CH

CH2

H2C

CH

CH2

CH3

HermanStaudinger

Longchainmolecule
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(naturalrubber)

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
n

Monomer=styrene
n<20 Oligomer
n>20 Polymer
Monomer units
Structural units=buildingblock
Repeating units=shortestrepeatingsequence
34

Terminology

Polystyrene
n

Poly(vinylalcohol)
CH2 CH
n
OH

StructuralUnit=RepeatingUnit
H2C

CH

StructuralUnit=RepeatingUnit
CH2 CH
OH
35

Terminology
Polymer:
poly(ethyleneterephthalate)PET

OCH2CH2O

OH
n

Monomers

O
HO C

HO CH2 CH2 OH
Ethyleneglycol

Repeatingunit:

Structuralunits

OCH2CH2O

OCH2CH2O

O
C OH

Terephthalicacid

C
O

36

Terminology

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

pendantgroups
endgroups
37

Terminology
Degreeofpolymerization
x=Numberofstructural units/chains
Poly(vinylchloride)
X CH2 CH Y
Cl 100

x=100

Poly(ethyleneterephthalate)
H

OCH2CH2O

x=2100=200

OH
100

OCH2CH2O

38

Terminology
Molecularweight
M=xMo+M(endgroups)

Mo=averagemolecular
weightofthestructuralunit

CH2 CH
Cl

X CH2 CH Y
Cl 100

M=10062.5+M(e.g.)

Structuralunit
(Mo=62.5g.mol
H

OCH2CH2O

OH

M=20096+M(e.g.)

100

OCH2CH2O

(60g.mol)

(132g.mol)

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

39

Terminology

Officialmethod:
H

OCH2CH2O

OH

M=20096+M(e.g.)

100

OCH2CH2O

(60g.mol)

(132g.mol)

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

Unofficialmethod:
M=10060+100132+M(e.g.)=20096+M(e.g.)

Ethyleneglycol

Terephthalicacid

(62g.mol)

(166g.mol)
40

Terminology
Thefunctionalityfofmonomeristhenumberofbondsformedinthe
reaction.Itmaydependonthepolymerizationreactionconditions.
H

O
n H 2N

amine

C OH

acid

H N

O
R

C OH +(n-1)H2O
n

polyamide

Thefunctionalityf=2.

41

Terminology
Thefunctionalityfofmonomerdependsonthepolymerizationreaction.
H2C CH

H2C CH

H2C CH n
n
H2C CH n

f=2

f=4

f=2

42

Terminology
Structure
Linearchain

Branched
Comb

Ladder

(DNA)

Network

Dendritic(tree-like)
43

Polymerization Reactions
Condensationpolymerization

O
n HO CH2 CH2 OH +n H3CO C
H

OCH2CH2O

O
C OCH3

OH

+(2n1)CH3OH

Smallmoleculeelimination,functionalgroupsinthebackbone

Additionpolymerization
n CH2 CH2

CH2 CH2 n
Noeliminationofsmallmolecules
openingofdoublebondsCCbackbone

44

Exceptions
Polyurethanes
(diol)
nHOR1OH+n O

(di-isocyanate)

C N R2 N C O
(polyurethane)
O H

H O

O R1 O C N R2 N C

n
Condensationpolymerizationwithno
eliminationofsmallmolecule.

Polyoxides
O
n CH2 CH2

CH2 CH2 O

Additionpolymerization
withoxygenatomsinthe
backbone.
45

Copolymers

Copolymersaremadeofatleasttwodifferentrepeatingunits.
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

Copolymersaremadeofatleasttwodifferentrepeatingunits.
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(vinylchloride)PVC

CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH

Cl
Cl
Cl
Cl
Cl
Cl
Cl
(semicrystallinepolymer)

Randomcopolymer:Poly(vinylchloride-co-vinylacetate)
CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH CH2 CH
Cl
OAc
Cl
OAc
OAc
Cl
Cl
(lesscrystalline,moreflexible,andopticallyclearerpolymer)

Alternatingcopolymer:Poly(styrene-alt-maleicanhydride)

CH2 CH CH CH CH2 CH CH CH CH2 CH CH CH

O O O

O O O

(polymericsurfactant)

O O O
48

Copolymers
Poly(ethyleneterephthalate)(PET)isacondensationhomopolymer.
O
HO CH2 CH2 O C

O
C O CH3
n

(samerepeatingunit)

Poly(ethyleneterephathlate-co-butyleneterephthalate)isacopolymer.
O
C4H8 O C

O
C O

O
CH2 CH2 O C
p

repeatingunit#1

O
C O
n

repeatingunit#2
49

Nomenclature

Non-systematicnamesaremostlyused.
SystematicnamesfromIUPAC:
Styrene(mostlyused)
Ethenylbenzene(inchemicalabstract)
Vinylbenzene(inolderchemicalabstract)
Phenylethylene(IUPAC)

50

MechanicalSterngth

Polymer Molecular Weight

MW2
MW1

MWo

PolymerMolecularWeight
MW < MWo 1,000 g.mol : Thepolymerhasnomechanicalstrength.
Thechanceisthatitisaliquid.
MWo < MW < MW1 5,000 10,000 g.mol : Thepolymerdevelops
mechanicalstrength.AtMW1,polymerentanglementsbegintoform.
MW1 < MW < MW2 : Mechanicalstrengthimprovesasmore
entanglementsaregenerated.
51
MW2 < MW : Asufficientnumberofentanglementshasbeenformed

Threethingsmakepolymerdifferentwithsmallmolecules
1)Summationofintermolecularforces
2)Chainentanglement
4)Timescaleofmotion

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.

CH4Wax:CnHn+2(n<100)Polyethylene(C2H4)n

53

Amorphouscrystallinepolymers

Thermoplastic,thermoset;elastomer,fiber
Entangledpolymersarecharacterizedwitheffectiveinternal
scale,commonlyknownasthelengthofmacromoleculebetween
adjacententanglementsMe.

54

Reptation

Entanglementswithotherpolymerchainsrestrict
polymerchainmotiontoathinvirtualtubepassing
throughtherestrictions.Withoutbreakingpolymer
chainstoallowtherestrictedchaintopassthroughit,
thechainmustbepulledorflowthroughthe
restrictions.Themechanismformovementofthe
chainthroughtheserestrictionsiscalledreptation.

Torelax,thepolymeric
materialmustwaitaperiod
repforthechaintomove
outofitstube.

repdependsofthe
chainsize
55

Reptationtheorydescribestheeffectofpolymerchain
entanglementsontherelationshipbetweenmolecularmassand
chainrelaxationtime(orsimilarly,thepolymerszero-shear
viscosity).Thetheorypredictsthat,inentangledsystems,the
relaxationtimeisproportionaltothecubeofmolecularmass,
M:~M3.Thisisareasonableapproximationoftheactual
observedrelationship,~M3.4.

56

Effect of Polymer Concentration

individual
polymercoils

overlap
concentration

entanglements

57

58

Polymer Characterization
MolecularMass:GPC,SLS,endgroupanalysis,etc.
Molecular Structure: ultraviolet-visible spectroscopy,
infrared spectroscopy, Raman spectroscopy, nuclear
magnetic resonance spectroscopy, electron spin resonance
spectroscopy,andmassspectrometry
Morphology:TEM,WAXS,SAXS
Thermalproperties:Tg,Tc,Tm
Mechanicalandviscoelasticproperties
59

Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
techniqueusedtodetermineTgandTmforpolymers.

heater

heater

TheDSCisheatedataconstantrate(10oC/minis
typical).Thecomputercontrolsthetemperaturein
bothsampleholdersbyadjustingtheamountofheat
flowingthroughtheheater.Differenceintheheat
flowsgoingthroughbothheatersindicatesthatthe
sampleisgoingthroughatransition.

60

Glass Transition

Heat flow

Differential Scanning Calorimetry (DSC) is a well-established

techniqueusedtodetermineTgandTmforpolymers.

semi-crystalline
material

melt

melt

glass
Tg

Tc

Tm
Temperature

HeatflowfromDSCtosample
61

Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
techniqueusedtodetermineTgandTmforpolymers.

Heat flow

Tg:AtTg,localmotionofthechainsisenabled.Forlocal
motionofthechainstobeenabled,heatmustbeprovidedto
thesample(heatflowsfromDSCtosample:positiveheat
flow).
Tc:WhenheatedaboveTg,thechainsexperienceenough
freedomsothatsomeoftheirpartscanarrangethemselves
intomicrocrystals.Crystallizationreleasesheat.Heatflows
fromsampletoDSC:negativeheatflow.
Tm:Asthetemperatureincreasesfurther,themelting
temperature(Tm)isreachedandthemicrocrystalsmelt.For
thistohappen,thesampleneedstoabsorbheatandheatflows
fromDSCtosample:positiveheatflow.
TransitionsobservedbyDSCoccuroverarangeof
temperatures.

heater

Tg

Tc

heater

Tm
Temperature
62

Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
techniqueusedtodetermineTgandTmforpolymers.

Heat flow

Tg:AtTg,localmotionofthechainsisenabled.Forlocal
motionofthechainstobeenabled,heatmustbeprovidedto
thesample(heatflowsfromDSCtosample:positiveheat
flow).
Tc:WhenheatedaboveTg,thechainsexperienceenough
freedomsothatsomeoftheirpartscanarrangethemselves
intomicrocrystals.Crystallizationreleasesheat.Heatflows
fromsampletoDSC:negativeheatflow.
Tm:Asthetemperatureincreasesfurther,themelting
temperature(Tm)isreachedandthemicrocrystalsmelt.For
thistohappen,thesampleneedstoabsorbheatandheatflows
fromDSCtosample:positiveheatflow.
TransitionsobservedbyDSCoccuroverarangeof
temperatures.

heater

Tg

Tc

heater

Tm
Temperature
63

Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
techniqueusedtodetermineTgandTmforpolymers.

Heat flow

Tg:AtTg,localmotionofthechainsisenabled.Forlocal
motionofthechainstobeenabled,heatmustbeprovidedto
thesample(heatflowsfromDSCtosample:positiveheat
flow).
Tc:WhenheatedaboveTg,thechainsexperienceenough
freedomsothatsomeoftheirpartscanarrangethemselves
intomicrocrystals.Crystallizationreleasesheat.Heatflows
fromsampletoDSC:negativeheatflow.
Tm:Asthetemperatureincreasesfurther,themelting
temperature(Tm)isreachedandthemicrocrystalsmelt.For
thistohappen,thesampleneedstoabsorbheatandheatflows
fromDSCtosample:positiveheatflow.
TransitionsobservedbyDSCoccuroverarangeof
temperatures.

heater

Tg

Tc

heater

Tm
Temperature
64

Glass Transition
Differential Scanning Calorimetry (DSC) is a well-established
techniqueusedtodetermineTgandTmforpolymers.

Heat flow

Tg:AtTg,localmotionofthechainsisenabled.Forlocal
motionofthechainstobeenabled,heatmustbeprovidedto
thesample(heatflowsfromDSCtosample:positiveheat
flow).
Tc:WhenheatedaboveTg,thechainsexperienceenough
freedomsothatsomeoftheirpartscanarrangethemselves
intomicrocrystals.Crystallizationreleasesheat.Heatflows
fromsampletoDSC:negativeheatflow.
Tm:Asthetemperatureincreasesfurther,themelting
temperature(Tm)isreachedandthemicrocrystalsmelt.For
thistohappen,thesampleneedstoabsorbheatandheatflows
fromDSCtosample:positiveheatflow.
TransitionsobservedbyDSCoccuroverarangeof
temperatures.

heater

Tg

Tc

heater

Tm
Temperature
65

Glass Transition

Heat flow

HowwouldtheDSCplotofasampleofatacticpolystyrenelooklike?

semi-crystalline
material

melt
glass
Tg

Tc

melt
atactic
polystyrene

Tm
Temperature

66

Glass Transition

Heat flow

InaDSCexperiment,thetemperatureischangedataknownrate(=
dT/dt).Theheatflow(HF=q/dt)ismonitored.TakingtheratioHF/
yieldsq/dT.
1stlawofthermodynamics:dH=q+VdP
Sincetheexperimentisconductedatconstantpressure,dP=0and
dH=qCpdT
Puttingitalltogether,onefindsthatCp=q/dT=HF/

semi-crystalline
material

melt

melt

glass
Tg

Tc

Tm
Temperature

67

Glass Transition
Intramolecular parameters
Theglasstransitionindicatestheonsetofsegmentalmotions.Segmentalmotionscanbe
visualizedwiththecrankshaftmechanismwhichallowssectionsofthechaintorelaxwithout
involvinglargescalemotionsoftheentirechainfoundintheviscousregionofthestress-strain
curve.

Thecrankshaftmechanismisenabledbyrotationofthebackbonebondsaboutoneanother.The
substituentsonthebackbonechainatomshinderrotationaroundthebackbonebondsduetosteric
hindranceandconstituteabarriertointernalrotation.
cis gauche skewed
trans gauche skewed
cis

Potential Barrier

vinylpolymer

68

Glass Transition
Theglasstransitiontemperature(Tg)isthemostimportantsingle
parameterthatdetermineswhatagivenamorphouspolymerwill
beusedfor.
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(ethyleneterephthalate)

-O-CH2-CH2-O-CO-C6H4CO-

+61

Poly(vinylchloride)

-CH2-CHCl-

+81

Polystyrene

-CH2-CH(C6H5)-

+100

Poly(methylmethacrylate)

-CH2-C(CH3)(CO2CH3)-

+105
69

Glass Transition
Question:Whichpolymerwouldyouusetomakeawindow?

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(ethyleneterephthalate)

-O-CH2-CH2-O-CO-C6H4CO-

+61

Poly(vinylchloride)

-CH2-CHCl-

+81

Polystyrene

-CH2-CH(C6H5)-

+100

Poly(methylmethacrylate)

-CH2-C(CH3)(CO2CH3)-

+105
70

Glass Transition
Question:Whichpolymerwouldyouusetomakeawindow?

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(ethyleneterephthalate)

-O-CH2-CH2-O-CO-C6H4CO-

+61

Poly(vinylchloride)

-CH2-CHCl-

+81

Polystyrene

-CH2-CH(C6H5)-

+100

Poly(methylmethacrylate)

-CH2-C(CH3)(CO2CH3)-

+105
71

Glass Transition
Question:Whichpolymerwouldyouusetomakeawindow?

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(ethyleneterephthalate)

-O-CH2-CH2-O-CO-C6H4CO-

+61

Poly(vinylchloride)

-CH2-CHCl-

+81

Polystyrene

-CH2-CH(C6H5)-

+100

Poly(methylmethacrylate)

-CH2-C(CH3)(CO2CH3)-

+105
72

Glass Transition
Question: Which polymer would you use to make a rubber
band?
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(ethyleneterephthalate)

-O-CH2-CH2-O-CO-C6H4CO-

+61

Poly(vinylchloride)

-CH2-CHCl-

+81

Polystyrene

-CH2-CH(C6H5)-

+100

Poly(methylmethacrylate)

-CH2-C(CH3)(CO2CH3)-

+105
73

Glass Transition
Question: Which polymer would you use to make a rubber
band?
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(ethyleneterephthalate)

-O-CH2-CH2-O-CO-C6H4CO-

+61

Poly(vinylchloride)

-CH2-CHCl-

+81

Polystyrene

-CH2-CH(C6H5)-

+100

Poly(methylmethacrylate)

-CH2-C(CH3)(CO2CH3)-

+105
74

Glass Transition
Question: Which polymer would you use to make a rubber
band?
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(ethyleneterephthalate)

-O-CH2-CH2-O-CO-C6H4CO-

+61

Poly(vinylchloride)

-CH2-CHCl-

+81

Polystyrene

-CH2-CH(C6H5)-

+100

Poly(methylmethacrylate)

-CH2-C(CH3)(CO2CH3)-

+105
75

Glass Transition
Polyethylene is an interesting case. Its Tg equals 125 oC, yet PE is
sufficientlyrigidtobeusedextensivelyforpackagingapplications.

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(ethyleneterephthalate)

-O-CH2-CH2-O-CO-C6H4CO-

+61

Poly(vinylchloride)

-CH2-CHCl-

+81

Polystyrene

-CH2-CH(C6H5)-

+100

Poly(methylmethacrylate)

-CH2-C(CH3)(CO2CH3)-

+105
76

Glass Transition
Polyethyleneisaninterestingcase.ItsTgequals125oC,yetPEissufficientlyrigidto
be used extensively for packaging applications. The rigidity of PE is due to PE
microcrystalswhichbindthechaintogetherandinhibitflow.T mforPEequals
+120oC.
Defects which hinder crystallization lower the rigidity of PE. Thus high density
polyethylene(HDPE)ismorerigidthanlowdensitypolyethylene(LDPE).

Cp = Heat flow /

DSCtraceforpolyethylene
semi-crystalline
material

melt

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
Thetensiletestmeasuresthe
resistanceofamaterialtoastatic
orslowlyappliedforce.Thedata
obtainedfromthetensiletests
describesmanymechanical
featuresofthepolymer.
78

Stressstrain relationship
thermoplasticpolymer

79

Amorphouspolymers

there is a drop in stress beyond the yield

point.Thisisbecausetheinitiallytangled
andintertwinedchainsbecomestraightand
untangled.Oncethechainsarestraighten,
additional stress causes necking, in which
there is the continued sliding and
deformationofthechains

80

Semi-crystallinepolymers

Itisonlydifferentfromanamorphousstress-straincurve
becauseitlacksthedrawingregion.

81

82

Definition Description
YieldPoint(strength):Yieldpointisthefirstpoint(load)at
whichthespecimenyields.Thisiswhenthespecimen'scrosssectionalareabeginstodecrease.Thisiscallednecking.

ModulusofElasticity:Theratioofstresstostrainwithinthe
elasticregionofthestress-straincurve.
YieldElongation:Thestrainattheyieldpoint.
ElasticRegion:Theportionofthecurvebeforetheyieldpoint.
PlasticRegion:Theportionofthecurveaftertheyieldpoint
Ultimate(tensile)strength:themaximumstressamaterialcan
withstandbeforefailing.
Ultimateelongation:Thetotalelongationjustbeforefracture

83

Viscoelastic properties of polymers

How do materials behave when deformed ?

Elastic (Energy Stored)

Viscous (Energy Dissipated)

Viscoelastic
i.e. Polymers

85

Theprincipalmethodofmeasuringthematerialpropertiesofasystemiswith
atransducer.Atransducermeasurestheforceofthesysteminresponsetoa
perturbationbythemotor,whichappliedeitheraknownstressandmeasured
theresultantstrain,orvice-versa.
thestressisequaltotheforceperunitarea,itisclearthatincreasingthearea
ofthefixturewillincreasetheforceexperiencedbythetransducer.
Forsystemswithextremelylowviscosities,thesurfaceareaismaximized,as
canbeseenwiththeconcentriccylinderset-up.Astheviscosityincreases,the
arearequirementisdecreased,withseveraldifferentsizefixturesforconeand
plateandparallelplateavailablebasedonthesystemrequirements.

86

Dynamic Oscillatory Measurements

Strain

Strain Controlled
Rheometer

Stress

Elastic

=0
TopPlate
Viscoelastic

Sample
BottomPlate

0 < < 90
Viscous

= 90
PhaseangleorTanDelta(thetangentofthephaseangle)isrelatedto,andis
anindicatorofmagnitudesofelasticity.

88

Therheologicalbehaviourofpolymericsystemsis
profoundlyinfluencedbytheirmolecularweights
andmolecularweightdistributions.
Thisinformationcanbederivedfromthecross-over
pointsforGandG
Zero-shearviscosityandtherelationshipbetween
viscosityandfrequency.
89

90

Makingisothermalmeasurementsoverarangeoffrequenciescangivea
valuableinsightintoapolymers'structurethroughthestudyoftheresultant
rheologicalresponses.
DataofmostinterestderivedfromafrequencysweepareComplexViscosity
(h*),StorageandLossmodulus(G'&G"),andPhaseangle().
ThepointatwhichtheG'&G"curvescrossoverisanexcellentindicatorof
magnitudesofaveragemolecularweightandmolecularweightdistribution
whencomparingsamples-thelowerdownthefrequencyrangethecurves
cross,thehighertheaveragemolecularweightandthepositionofthecrossoveronthemodulusaxisgivesanindicationofmolecularweightdistribution
(increasedmodulus=narrowerMolecularweightdistribution).

91

theplotgivesavirtuallylinearresponseacrosstheninegrades
whichrepresentedtherangeofMwcommerciallyavailable-
thusgivingauseful'lookup'charttocomparefutureHDPE
rheologicalmeasurementsagainsttoprovideanindicationof
magnitudeofMw.
92

TheviscosityplateauatahigherfrequencysuggestsnarrowerPDI93
Thehigherzeroshearviscosity,thelargermolecularweight

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. (tensilebehaviour)
Viscoelastic properties. (G, G, Tan delta)

94