2.

StructuresandBulkPropertiesof
Biomaterials Biomaterials
Objective
Tounderstandthedifferentstructuresofpolymers,
metals,andceramicsandhowthestructuresare ,
relatedtotheirbulkproperties.
1
Metal
TheFramework
BioMaterials BioMaterials
Metal
Ceramics
Polymer
Structure
Cell
Characterization
Protein
Property
Biological
Response
Cell
Immunity
Bulk
Response
Surface Degradation
Blood
Bulk Surface Degradation
Pathogen
2
2.1Polymers
3
Whatispolymer?
POLY MER
POLY=MANY MEROS=PARTS
polymer
mer
RepeatunitMer (thesmallestbuildingblockofapolymer):a
structural entity composed of a fixed number of atoms in a given structuralentitycomposedofafixednumberofatomsinagiven
structurethatisrepeatedoverandovertoformthepolymer.
A molecule containing only one mer is a monomer Amoleculecontainingonlyonemer isamonomer
4
M i M i
Polyvinylchloride(PVC)
Polypropylene(PP)
Mer unit Mer unit
Monomer
structure
Polymers are mostly named after their monomers. Polymersaremostlynamedaftertheirmonomers.
5
Polyethylene Poly(tetrafluoroethylene)
Polystyrene
y y
(PE)
(PTFE)
(PS)
l (2 h d th l poly(2hydroxyethyl
methacrylate)
Poly(methyl
methacrylate)(PMMA)
polylactide polylactide
6
7
Howtodefinethestructureofpolymers?
8
Polymers:MolecularWeight
DegreeofPolymerization:numberofrepeatunitsinapolymer,indicatedby
theletterninthechemicalformulaforthepolymer.
=
Degreeof
polymerization
Molecularweight
of the repeat unit

Molecularweight
of the polymer
TheNumberof
repeating unit polymerization oftherepeatunit ofthepolymer repeatingunit
Molecularweightofpolymershasa
distribution
9
AverageMolecularWeight
n
M
Numberaveragemolecularweight()
N

=
i
i
i
N
N
xi
xi:numberfraction

= =
i
i
i
i i
i
i i n
N
M N
M x M
w
M Weightaveragemolecularweight( )

i
i i
M N
M w M
2
i
W
i
i i i
M N W =

= =
i
i i
i
i
i i w
M N
M w M

=
i
i
i
W
W
wi
Polydispersity index (PI) smallest
wi:weightfraction
w
M
PI
Polydispersity index(PI):smallest
possiblePIis1.00
n
w
M
PI =
10
Sample Molecular Weight Number of Chains
Agivenpolymersampleisamixtureofthreesamples:
Sample MolecularWeight NumberofChains
1 5,000 1,000
2 10,000 1,000 , ,
3 1,000,000 3
(a)Calculatethenumberaveragemolecularweightofthepolymer ( ) g g p y

[ ] ) 3 1000 1000 ( ) 1000000 3 ( ) 10000 1000 ( ) 5000 1000 ( + + + + =

n
M

= =
i
i
i
i i
i
i i n
N
M N
M x M
] / 1 1 : [ 8987 mole g Da Note Da = =
(b)Calculatetheweightaveragemolecularweightofthepolymer
[ ] )] 1000000 3 ( ) 10000 1000 ( ) 5000 1000 [( ) 1000000 ( 3 ) 10000 ( 1000 ) 5000 ( 1000
2 2 2
+ + + + =
w
M

= =
i
i i
i
i i
i
i i w
M N
M N
M w M
2
Da 173611 =
11

i
i i
Howtodeterminethemolecularweight
ofpolymers?
Size Exclusion Chromatography (SEC) SizeExclusionChromatography (SEC)
Chromatographyisthecollective
termforasetoflaboratory
techniquesfortheseparationof
mixtures.Themixtureisdissolvedin
afluidcalledthemobilephase,
whichcarriesitthroughastructure
holding another material called the
mobile
phase
holdinganothermaterialcalledthe
stationaryphase. Thevarious
constituentsofthemixturetravelat
different speeds causing them to
stationary
phase
differentspeeds,causingthemto
separate.Theseparationisbasedon
differentialpartitioningbetween
h bil d i h
effluent
themobileandstationaryphases.
12
SEC:SeparationMechanism
SEC columns are filled with small (diameter about 10 m) porous beads SECcolumnsarefilledwithsmall(diameterabout10m)porous beads
Moleculesareseparated basedonthedifferenceintheirretentiontimeinthe
porousstationaryphase:themoleculewiththelargestsizefirstexitthe
h d h ll l l l stationaryphase,andthesmallestmoleculesexistslast
Retentiontime
Sizeofthe
polymerchain
Retentiontime(min)
Molecularweight
0
Retentiontime isthetime
requiredforasoluteto
migrate, or elute, from the migrate,orelute,fromthe
column(fromtheinstant
ofsampleinjectiontothe
pointatwhichthepeak p p
maximumoccurs).
13
SEC:Instrumentation
Pumpdrivescirculationofthemobile
phase phase
Injector injects a given amount of Injector injectsagivenamountof
sampleintothemobilephase
C l t diff t i d Columnseparatesdifferentsized
moleculesbasedonretention
time time
Detectortranslatestheamountof
l t i th bil h t analyteinthemobilephasetoan
detectiblesignal(UVvis,Mass
spectroscopy,.) spectroscopy,.)
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SEC:Instrumentation
porous beads
Detector1
mobilephase
porousbeads
Detector2
p
Photo
Column
Pump Injector
15
SEC:Measurement
)
MWofthe
unknownsample
e
i
g
h
t

(
D
a
)
calibrationcurve
e
c
u
l
a
r

w
e
M
o
l
l d d h k l l h ( )
Retentiontime(min)
1.Runpolymerstandardswithknownmolecularweight(MW)
2.Createacalibrationcurve(MWofthepolymerstandardsagainsttheir
retention time) retentiontime)
3.RuntheunknownsampleandreadoutitsMWfromthecalibrationcurve
16
Indepthquestion:
one st dent had a SEC training to meas re a pol mer sample onestudenthadaSECtrainingtomeasureapolymersample
withnarrow,symmetricmolecularweightdistribution.
He made two measurements In the first measurement he did the Hemadetwomeasurements.Inthefirstmeasurement,hedidthe
measurementrightafterpreparingthepolymersolution.Beforethe
secondmeasurement,heleftthepolymersolutionmagneticallystirred
i f h d i h i h l i i l A i h ibl SEC infumehoodwithoutcappingthesolutionvial.AssignthepossibleSEC
curvesbelowtothetwomeasurementsandexplainyourassignments.
Polymer:Tacticity
Homopolymers: polymers with one type of repeat unit Homopolymers:polymerswithonetypeofrepeatunit.
Isotactic:TheR groupsarearrangedonthesame
sideofthechain
R:sidegroup
Syndiotactic:TheR groupsalternate positionson
either side of the chain eithersideofthechain
Atactic: The R groups are situated randomly
Polystyrene
Atactic:TheR groupsaresituatedrandomly
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Polystyrene
PolymerStructure
Li l th ti it j i d i d t d f hi Linearpolymer:therepeatingunitsarejoinedinanendtoendfashion.
Branchedpolymershavechainsbranchingoffthemainchain.
Crosslinked polymers:
adjacentchainsare
j i d i i joinedatcertainpoints
viacovalentbonds,
forming a three formingathree
dimensionalnetwork
19
Copolymers involve twoormorerepeatunittypes
Randomcopolymer(twomer unitsaredistributedalongthechainwithnopattern)
Alternatingcopolymer (mer typesalternatealongthechain)
Blockcopolymers(eachtypeofrepeatunitisclusteredinregionsalongthechain)
Graftcopolymer(homopolymerchainsareattachedtoadifferenthomopolymer
main chain) mainchain)
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PolymersSynthesis
Addition(chainreaction)polymerization(e.g.,freeradicalpolymerization)
I iti ti ( ti ti f R I
k
d
Initiation (activationofa
monomerthroughchemical
reactions)
R
R + M M
1

I
k
d
Propagation (monomers
1
continuetosuccessivelyjoin
thepolymerchainand
increase its molecular weight )
M
n
+ M M
n+1

k
p
increaseitsmolecularweight)
T i ti (d t ti f
M + M M
k
t
Termination (destructionof
theactivesite:freeradical
coupling)
M
n
+ M
m
M
n+m
M + M M + M
k
t
21
M
n
+ M
m
M
n
+ M
m
PolymersSynthesis
Polyethylene y y
Leadingtopolymerswitha g p y
molecularweightdistribution
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PolymersSynthesis
Condensation(stepreaction)polymerization
Thepolymerizationoccursthrougheliminationofonemolecular
( ll d) (usuallywateroracid)
Theproductdoesnothavethesamechemicalformulaaseithermer
Typicalpolymers:nylonsandpoly(carbonates)
+ HCl
23
SynthesisofNylon6,10
Condensation (step reaction) polymerization Condensation(stepreaction)polymerization
http://www.youtube.com/watch_popup?v=yFEHKRdXb9Y&vq=medium
24
Howarepolymerchainsorganizedto
f i i l ? formmacroscopicmaterials?
25
PolymerCrystalStructures:Percentcrystallinity
ChainFoldedModelofCrystallinity
Lamellar
Polymerchainscanfoldtoformlamella
structure,whichisthebasicunitof
polymericcrystal.
Lamellar
chainfolded
crystallite
po y e c c ys a
Lamellar
chainfolded
Becauseofthelargesizeandflexibilityof
polymerchains,polymermaterialsarerarely
crystallite
Tiemolecule
p y , p y y
100%crystalline,eithersemicrystalline
(containingbothcrystallineandamorphous
regions)oramorphous.
Amorphous
region region
Insemicrystalline polymer,multipleintermingled
chainswhicheachhascrystallineregionslocated
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insidethelamellarstructuresandamorphous
regionsfoundoutside.
PolymerCrystalStructures:Percentcrystallinity
Factorsaffectingcrystallinity (anythingpreventchainalignment
or discourage secondary bonding between chains will reduce ordiscouragesecondarybondingbetweenchainswillreduce
polymercrystallinity)
Mer side groups (large side groups prevent neighboring chains from coming Mer sidegroups(largesidegroupspreventneighboringchainsfromcoming
closeenoughtoformacrystallinestructure.)
Chainbranching(branchedpolymershavelowerpercentcrystallinity)
Tacticity (atactic polymershavelowerpossibilitytocrystallizethanisotactic y ( p y p y y
orsyndiotactic polymers)
Regularity of mer placement in copolymers (alternating and block Regularityofmer placementincopolymers(alternatingandblock
copolymershaveahigherprobabilityoftheformationofcrystalline
regionsthanrandomcopolymers)
27
Compare crystallinity of the following polymers Comparecrystallinityofthefollowingpolymers
(A)
(B)
(C)
( )
28
Polymer:ThermalTransition
CrystallinepolymersundergomeltingatT
m
(meltingtemperature).Below
T
m
,thecrystallineregionsofthepolymersarehighlyordered,whileabove
it,polymerchainsshowrandomdistributionwithnolongrangeorder.
Melting occurswhen
thereareenoughatoms
h i orchainsegments
vibratingtoresultin
overallchainmotion.
Amorphouspolymerspossessglasstransitiontemperature(T
g
).Below p p y p g p (
g
)
T
g
,thepolymermaterialisglassyandbrittle,whileaboveit,thechains
aremobileenoughtoproducearubbery,elasticmaterial.
Glasstransitionoccurswhenthereisenoughenergytocausemolecular
motionaroundthepolymerbackbone.
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SemiCrystalline Polymer: Thermal Transition Semi CrystallinePolymer:ThermalTransition
Stiffness
Temperature
30
F t ff ti T ( thi di d FactorsaffectingT
m
(anythingdiscouragesecondary
bondingbetweenchainswilldecreaseT
m
)
Chainbranching(withmorebranchedchains,moleculesareless
denselypacked,leadingtopoorsecondarybondingbetweenthe
l l ) molecules)
MolecularWeight (Forpolymerswiththesamechemicalstructure,high g p y g
MWpolymershaveahigherT
m
)
PolymerswithlowerMWhavemorechainends.Becausechain
endsaremorefreetomovethanotherpartofthepolymer
molecule,itneedslessenergytoproducethemotionfor
polymerswithsmallerMW. p y
31
Compare T of the following polymers CompareT
m
ofthefollowingpolymers
(A)
(B)
32
F t ff ti T ( thi f h i ib ti d FactorsaffectingT
g
(anythingfavorschainvibrationand
rotationwilldecreaseT
g
)
Chainflexibility(polymerwithmoreflexiblechainsrequireless
energytoachievetherequiredmotionaroundthebackboneand
i T ill b l ) itsT
g
willbelower)
Bulkysidegroup(reducesthemovementaroundthebackboneand
increaseT
g
)
MolecularWeight (highMWpolymershaveahigherT
g
)
33
ThermalAnalysis:DifferentialScanning
C l i t (DSC) Calorimetry (DSC)
In DSC the difference in heat flow into a sample and InDSC,thedifferenceinheatflowintoasampleand
referencesampleisrecordedasafunctionoftemperature
whilethetwoareexposedtoacontrolledtemperature p p
ramp.
In heatflux DSC the sample and InheatfluxDSC,thesampleand
referenceareheatedfromthe
sameheaterandthe
temperature difference between temperaturedifferencebetween
thetwocellsismeasured.The
temperaturedifferenceisthen
d h fl convertedintoheatflow.
34
DSC thermogram DSCthermogram
T
m
T
g
35
Question: Assign the three thermograms Question:Assignthethreethermograms
(1,2,and3)tothethreepolymers.
36
In depth question: Indepthquestion:
compare the DSC thermograms of block comparetheDSCthermograms ofblock
copolymerandrandomcopolymerof
polyethylene and polystyrene polyethyleneandpolystyrene.
37