1

RichardE.Eitel
AssociateProfessor
Email:reitel@stevens.edu
Office:Burchard 307B
DepartmentofChemical
EngineeringandMaterials
Science
StevensInstituteofTechnology
E344:MaterialsProcessing
05 StructureandProperties
ofPolymers
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Thegoalofthisdiscussionistobeabletodescribethe
macromolecularstructureofpolymersandrelatethisto
theirengineeringproperties..
Bytheendofthisdiscussionyoushouldbeableto:
Describetheroleofpolymerchain
lengthonkeyengineering
properties.
Classifythebasicstructuresof
polymerchains.
Predicttrendsinthecrystallinity
andpropertiesofpolymerbasedon
theirmolecularweightandchain
structure.
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Polymersaregiantmacromoleculesconsistingof10sto
many1,000sofcovalentlybondedrepeat(mer)units.
mer
GuidedInquiryI:AverageMolecularWeight
(10minutes)
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A. 0.0012
B. 831.75
C. 832
D. 1,472,800
E. I don't know.
ConceptCheck:
What is the DP for polypropylene with a
molecular weight of 35,000 g/mol?
m.socrative.comRoom#129851
A. g
B. gmol
C. mol
D. It is unit less
E. I don't know.
ConceptCheck:
What are the units for DP?
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Thechainlengthofpolymersischaracterizedbythedegree
ofpolymerization(DP)andthemolecularweight.
PolymersareALWAYSmixtureofmacromoleculesof
varyingmolecularweights
NumberAverageMolecularWeight(H
n
):
Where:
H

isthemedianmolecularweightofachaininthei
th
sizerange.
x

isnumberfractionofchainsinthei
th
sizerange
w

isweightfractionofchainsinthei
th
sizerange
m ismolecularmassoftherepeat(mer)unit
M
n
= x
|
M
|
M
w
= w
|
M
|
=
x
|
M
|
M
|
x
|
M
|
=
x
|
M
|
2
x
|
M
|
WeightAverageMolecularWeight(H
w
):
Degreeofpolymerization(DP):
Polydispersity Index(PDI):
DP =
M
n
m
PDI =
M
w
M
n
0
0.05
0.1
0.15
0.2
0.25
F
r
a
c
t
i
o
n
a
l

C
o
n
t
e
n
t
MolecularWeightRange(g/mol)
FractionalDistrubtionofMolecularWeights
WeightFraction(wi)
NumberFraction(ni)
GuidedInquiryII:MolecularWeightCalculations
(8minutes)
Considerasampleofplasticwhichyouknowis15mol%polymer
moleculeswithmolecularweight500,000g/mol,and85mol%
polymermoleculeswithmolecularweight150,000g/mol.
NumberAverageMolecularWeight(H
n
):
H
n
= x

WeightAverageMolecularWeight(H
w
):
H
w
= w

=
x

=
x

2
x

Degreeofpolymerization(DP):
P =
H
n
m
Polydispersity Index(PDI):
PI =
H
w
H
n
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A. 119,600g/mol
B. 202,500g/mol
C. 280,000g/mol
D. Idontknow
ConceptCheck:
What is the number average molecular weight for
the above mixture?
m.socrative.comRoom#129851
A. 119,600g/mol
B. 202,500g/mol
C. 280,000g/mol
D. Idontknow
ConceptCheck:
What is the weight average molecular weight for
the above mixture?
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A.Yes
B. No
C. H
w
isalwayslessthanH
n
.
D.Idontknow
ConceptCheck#3:
Can M
w
belessthanM
n
?Why?
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Formanysimplelinearpolymers,materialpropertiesare
dictatedbychainlengthandweaksecondarybonding
betweenchains.
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GuidedInquiryIII:MWandProperties.
(5minutes)
Considertwodifferentplatesofspaghetti.Oneinwhichallthe
strandsarethefulllengthandoneinwhichthestrandhavebeen
cutintoshortsegments.
A. 100,000 g/mol
B. 200,000 g/mol
C. Theyhavethesamestrength.
D. Idontknow
ConceptCheck#4:
Which has a higher strength; polyethylene of
100,000 g/mol or 200,000 g/mol?
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ConceptCheck#5:
Which flows more easily; polyethylene of 100,000
g/mol or 200,000 g/mol?
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A. 100,000 g/mol
B. 200,000 g/mol
C. Theyflowequally.
D. Idontknow
Polymersmayalsobecharacterizedbychainlengthand
meanendtoendDistance.
Total(stretchedout)chainlength(L):
I = N J sin
0
2
Meanendtoenddistance(r):
r = J N
Where:
d bondlength
N numberofbondsinchain
anglebetweenadjacentatoms
=109.5
o
forCC
L
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Thepropertiesoflinearpolymerscanbemodifiedby
introducingbranchingorcrosslinking.
Linear
secondary
bonding
Branched
Cross-Linked Network
Likemetalsandceramicspolymersmayexhibithighly
orderedcrystallineregions.
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GuidedInquiryIV:PolymerCrystallinity.
(10minutes)
a) Polyethyleneorpolystyrene.
b) Polyethylenewithmanylongbranchesorpolyethylene
withafewshortbranches.
c) Atactic polypropyleneorisotacticpolypropylene.
d) Polypropyleneorpoly(ethyleneterephthalate)(PET).
e) Polyethyleneorarandomcopolymerof50%ethylene
repeatunitsand50%propylenerepeatunits.
f) PETmeltedandrapidlycooledtoroomtemperatureor
PETmelted,cooledto150 C,heldtherefor1hour,and
thencooledtoroomtemperature.
Reportout:
Which of the following pairs is more crystalline?
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Theproductionofmostpolymermacromoleculesfrom
theirmonomeroccursbyoneoftwopolymerization
routes.
Addition(Chaingrowth)
polymerization:
Condensation(stepreaction)
Polymerization
(byproductproducedoftenwater)
Initiator
monomer
Polyethylene:
Polyethyleneterephalate
Thermoplasticpolymersaretypicallylinearorslightly
branchedandsoftenonheatingallowingthemtobeeasily
(re)formedandreadilyrecycled.
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Thermosetpolymersreactonmixingorunderactionof
heatformingextensivecrosslinks.
Example: Bakelitefirstcompletely
syntheticplastic,1907.