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8/11/2019 2 Structure&Properties
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2.
Structures
and
Bulk
Properties
of
Objective Tounderstandthedifferentstructuresof polymers,
metals andceramicsandhowthestructuresare
relatedtotheirbulkproperties.
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TheFramework
BioMaterialsBioMaterials Ceramics
Polymer
Structure
Characterization Protein
Property BiologicalImmunityBlood
Pathogen 2
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2.1Polymers
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Whatispolymer?
POLY MER
POLY=MANY MEROS
=PARTS
polymer mer
RepeatunitMer(thesmallestbuildingblockofapolymer):a
structurethatisrepeatedoverandovertoformthepolymer.
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Polyvinylchloride(PVC) Polypropylene(PP)
er un t er un t
Monomer
structure
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Polyethylene Poly(tetrafluoroethylene) Polystyrene
(PE) (PTFE) (PS)
po y
y roxyet ymethacrylate) Poly(methylmethacrylate)(PMMA)ol lactide
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Howtodefinethestructureofpolymers?
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Polymers:MolecularWeight
Degreeof
Polymerization:numberofrepeatunitsinapolymer,indicatedby
thelettern inthechemicalformulaforthepolymer.
= DegreeofMolecularweight Molecularweight TheNumberof
Molecularweightofpolymershasa
distribution
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AverageMolecularWeight
nMNumberaveragemolecularweight( )
=
i i
i
Nxi xi:numberfraction
==i i
i ii
i iin
N
MxM
wMWeightaveragemolecularweight( )
i iiMN 2
W
iii NW =
==
i iii
iiw
MN
w
=
i iW
w wi:weightfraction
o y spers y n ex :sma es
possiblePIis1.00
nM
=
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Agivenpolymersampleisamixtureofthreesamples:
1 5,000 1,000
2 10,000 1,000
3 1,000,000 3
a Calculatethenumberavera emolecularwei htofthe ol mer
[ ] )310001000()10000003()100001000()50001000( ++++=nM
==
i i
i ii
i iin NNMxM]/11:[8987 molegDaNoteDa ==
(b)Calculatetheweightaveragemolecularweightofthepolymer
)]10000003()100001000()50001000[()1000000(3)10000(1000)5000(1000
222++++=
wM
==
ii
i ii
i iiw MN
MNMwM
2Da173611=
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Howtodeterminethemolecularweight
of
polymers?
Chromatographyisthecollective
termforasetoflaboratory
techniquesfortheseparationof
mixtures.Themixtureisdissolvedin
afluid
called
the
mobile
phase
,
whichcarriesitthroughastructuremobile
phase
stationaryphase.Thevarious
constituentsofthemixturetravelat
stationary
phase
,
separate.Theseparationisbasedon
differentialpartitioningbetween
effluent
t emo ean stat onaryp ases.
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SEC:SeparationMechanismSEC columns are filled with small diameter about 10 m orous beads
Moleculesareseparatedbasedonthedifferenceintheirretentiontimeinthe
porousstationaryphase:themoleculewiththelargestsizefirstexitthe
stationaryp ase,an t esma estmo ecu esexists ast
Retentiontime
Sizeofthe
polymerchain
Retentiontime(min)
Molecularweight
0
Retentiontimeisthetime
requiredforasoluteto
mi rate or elute from the
column(fromtheinstant
ofsampleinjectiontothe
ointatwhichthe eak
maximumoccurs).
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SEC:Instrumentation
Pumpdrivescirculationofthemobile
sampleintothemobilephase
o umnsepara es eren s ze
moleculesbasedonretention
Detectortranslatestheamountof
ana y e n emo ep ase oan
detectiblesignal(UVvis,Mass
,.
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SEC:Instrumentation
Detector1
mobile hase
Detector2
PhotoColumn
PumpInjector
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SEC:Measurement
MWof
the
unknownsample
ight(Da
calibrationcurve
ecularw
M
ol
Retentiontime(min)
1.Runpo ymerstan ar swit nownmo ecu arweig t MW
2.Createacalibrationcurve(MWofthepolymerstandardsagainsttheir
3.Run
the
unknown
sample
and
readout
its
MW
from
the
calibration
curve
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Indepthquestion:
one
s u en
a
a
ra n ng
o
measure
a
po ymer
samp e
withnarrow,symmetricmolecularweightdistribution.
. ,
measurementrightafterpreparingthepolymersolution.Beforethe
secondmeasurement,heleftthepolymersolutionmagneticallystirredn ume oo w t outcapp ngt eso ut onv a . ss gnt eposs e
curvesbelowtothetwomeasurementsandexplainyourassignments.
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Polymer:Tacticity .
Isotactic:TheRgroupsarearrangedonthesame
sideofthechain
R:sidegroup Syndiotactic:TheRgroupsalternatepositionson
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PolymerStructure
near
po ymer:t erepeat ngun tsare o ne nanen toen as on.
Branched
polymers
havechainsbranchingoffthemainchain.
Crosslinked polymers:
adjacentchainsare
o ne atcerta npo nts
viacovalentbonds,
dimensionalnetwork 19
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Copolymersinvolvetwoormorerepeatunittypes
Randomcopolymer
(twomer unitsaredistributedalongthechainwithnopattern)
Alternating
copolymer(mer typesalternatealongthechain)
Blockcopolymers(eachtypeofrepeatunitisclusteredinregionsalongthechain)
Graftcopolymer(homopolymerchainsareattachedtoadifferenthomopolymer
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PolymersSynthesis
Addition(chain
reaction)
polymerization
(e.g.,
free
radical
polymerization)
kdn a on ac va ono a
monomerthroughchemical
reactions) R + M M
kd
Propagation(monomers
continuetosuccessivelyjointhepolymerchainand
increase its molecular wei ht
Mn + M Mn+1p
kterm na on es ruc ono theactivesite:freeradical
coupling)
n m n+m
kt
21
n
m n
m
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PolymersSynthesis
Pol eth lene
Leadin to ol merswitha
molecular
weight
distribution 22
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PolymersSynthesis
Condensation(step
reaction)
polymerization
Thepolymerizationoccursthrougheliminationofonemolecular
usua ywateroraci
Theproductdoesnothavethesamechemicalformulaaseithermer
Typicalpolymers:nylonsandpoly(carbonates)
+ HCl
23SynthesisofNylon6,10
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http://www.youtube.com/watch_popup?v=yFEHKRdXb9Y&vq=medium
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How
are
polymer
chains
organized
to
ormmacroscop cmater a s
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PolymerCrystalStructures:Percentcrystallinity
ChainFolded
Model
of
Crystallinity
Polymerchainscanfoldtoformlamella
structure,whichisthebasicunitof
ol mericcr stal.
chainfolded
crystallite
Lamellar
chainfolded
Becauseofthelargesizeandflexibilityof
ol merchains, ol mermaterialsarerarel
crystallite
Tiemolecule
100%crystalline,eithersemicrystalline
(containingbothcrystallineandamorphous
regions)oramorphous.
Amorphous
Insemicrystallinepolymer,multipleintermingled
chainswhicheachhascrystallineregionslocated
26
insidethelamellarstructuresandamorphous
regionsfound
outside.
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PolymerCrystalStructures:Percentcrystallinity
Factorsaffectingcrystallinity(anythingpreventchainalignment
polymercrystallinity)
closeenoughtoformacrystallinestructure.)
Chainbranching(branchedpolymershavelowerpercentcrystallinity)
Tacticity(atactic polymershavelowerpossibilitytocrystallizethanisotactic
orsyndiotactic polymers)
copolymershaveahigherprobabilityoftheformationofcrystalline
regionsthanrandomcopolymers)
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Com are cr stallinit of the followin ol mers
(A)
B
(C)
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Polymer:ThermalTransition
Crystalline
polymers
undergomelting
at
Tm(meltingtemperature).BelowTm,thecrystallineregionsofthepolymersarehighlyordered,whileabove
it,polymerchainsshowrandomdistributionwithnolongrangeorder.
Meltingoccurswhen
thereareenoughatomsorc a nsegments
vibratingtoresultin
overallchainmotion.
Amorphouspolymerspossessglasstransitiontemperature(T ).Below
Tg,thepolymermaterialisglassyandbrittle,whileaboveit,thechains
aremobileenoughtoproducearubbery,elasticmaterial.
Glasstransitionoccurswhenthereisenoughenergytocausemolecular
motionaroundthepolymerbackbone.
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Stiffness
Temperature
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ac ors
a ec ng
m any ng
scourage
secon ary
bondingbetweenchainswilldecreaseTm)
Chainbranching(withmorebranchedchains,moleculesareless
denselypacked,leadingtopoorsecondarybonding
between
the
mo ecu es
MolecularWeight(Forpolymerswiththesamechemicalstructure,high
MWpolymershaveahigherTm)
PolymerswithlowerMWhavemorechainends.Becausechain
endsaremorefreetomovethanotherpartofthepolymer
molecule,itneedslessenergytoproducethemotionfor
ol merswithsmallerMW.
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m
(A)
(B)
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ac orsa ec ngg
any ng avorsc a nv ra onan
rotationwilldecreaseTg)
Chainflexibility(polymerwithmoreflexiblechainsrequireless
energytoachievetherequiredmotionaroundthebackboneandts gw e ower
Bulkysidegroup(reducesthemovementaroundthebackboneand
increaseTg)
MolecularWeight(highMWpolymershaveahigherTg)
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ThermalAnalysis:DifferentialScanning
a or me ry ,
referencesampleisrecordedasafunctionoftemperature
whilethetwoareex osedtoacontrolledtem erature
ramp.
,
referenceareheatedfromthesameheaterandthe
thetwocellsismeasured.The
temperaturedifferenceisthen
converte into eat ow.
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Tm
Tg
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