BiomaterialsLecture12

Surfaces:SurfaceTensionandYoung
LaplaceEquation
Unlessotherwisenoted,sourceInformationforthefollowingslides:
1) B.Ratner,A.Hoffman,F.Schoen,andJ.Lemons:BiomaterialsScience,
2
nd
edition(SanDiego:ElsevierAcademicPress.2004).
2) Butt,HJ.;Graf,K.;Kappl PhysicsandChemistryofInterfaces,2
nd
Edition
(WiletVCH:Weinheim 2006).
TodayIproposetotellyouofarealtwo
dimensionalworldinwhichphenomena
occurthatareanalogoustothosedescribed
inFlatland.Iplantotellyouaboutthe
behaviorofmoleculesandatomsthatare
heldatthesurfaceofsolidsandliquids.
I.Langmuir,Science 1936,84,379.
In1932hereceivedtheNobelPrizeinChemistry"forhisdiscoveries
andinvestigationsinsurfacechemistry.
1
st
industrialscientisttowintheNobelPrize
SurfacesofBiomaterials
Whyaresurfacesimportantinbiomaterials
applications?
Thesurfaceofamaterialstronglydictates
performanceinvivo
SurfacePropertiesInfluencingCellAdhesion
Wettability
Roughness
ElectricalCharge
Crystallinity
Composition
Mobility
Whatconstitutesasurface?
Aninterface istheboundaryregionbetweentwoadjacentbulkphases
Werecognize(S/G),(S/L),and(L/V)assurfaces
L
L
V
G
S
S
L
L
L=Liquid
G=Gas
S=Solid
V=Vapor
S
S
Werecognize(S/G),(S/L),and(L/V)assurfaces
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Whatssospecialaboutasurface?
1. Inherentlysmallnumberofatoms
a) Bulkvs.Surface
1cm
3
material
10
23
atoms
Surface10
15
atoms
Modifiedfrom:Anne Mayes3.051J/20.340JMaterialsforBiomedicalApplication,MIT,http://ocw.mit.edu,
Whatssospecialaboutasurface?
2. Enhancedmobility
a) Fewerbonds
b) Gradientindensity
Facilitatesratelimitedprocesses(phasetransformations,
crystallization,corrosion,)
Ideal2Dsurfacesexistonly
asmathematicconstructs
Modifiedfrom:Anne Mayes3.051J/20.340JMaterialsforBiomedicalApplication,MIT,http://ocw.mit.edu,
Whatssospecialaboutasurface?
3. Higherenergystate
Atoms/moleculeswithunsatisfied(dangling)or
strainedbonds
Highreacvityandsuscepbilitytoadsorbates
Modifiedfrom:Anne Mayes3.051J/20.340JMaterialsforBiomedicalApplication,MIT,http://ocw.mit.edu,
PhysicalDescriptionofBiomaterialSurfaces
Biomaterialsurfacesexhibitremarkableheterogeneityinphysicalstructure:
Materialdependant:Metalsvs.Polymersvs.Ceramicsvs.Gels
Chemistry:Polarvs.Apolar,Charge,Reactivity,Patterned
Morphology:Smooth,Rough,Stepped,Patterned,Diffuse
Order:Crystalline,Amorphous,SemiCrystalline,Phases
Environment:Hydration,SolventQuality
Bumpywith Phases
Hydration
Glassy
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CrystalSurfaceDefects
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CrystalSurfaceDynamics
PolymerSurfaceDynamics
Givensufficientmobility,polymersurfaceswillreorientorrestructurein
responsetotheirlocalmicroenvironmentsoastominimizetheirinterfacialfree
energywiththesurroundingphase.
CH
3
OH
CH
3
OH
CH
3
CH
3
OH
OH
OH OH
OH
OH
CH
3
CH
3
CH
3
CH
3
Bulk Bulk
PolarSolvent ApolarSolvent/Air
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BiologicalSurfaces
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SurfaceEnergetics
Moleculesinthebulkofamaterial(e.g.crystallattice)havealowrelativeenergy
stateduetonearestneighborinteractions(e.g.bonding).
Performingsufficientworkonthesystemtocreateaninterfacecandisruptthis
harmony...
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Moleculesatasurfaceareinastateofhigherfreeenergythanthoseinthebulk.
Thisisinlargepartduetothelackofnearestneighborinteractionsatasurface.
(Excess)SurfaceFreeEnergy
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Thesamethingoccursregardlessofmaterial(e.g.polymers).
(Excess)SurfaceFreeEnergy
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ImportantPoint
Systemsmovetowardloweringtheirfreeenergy
Surfacesdosoby:
Geometricchanges(ifpossible)
Bonding(strongandweakinteractions)
Dynamicrearrangement
Protein
CH
3
OH
CH
3
OH CH
3
OH
CH
3
OH
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SurfaceTension
Surfacetensionactstodecreasethefreeenergyofthesystem,hence
someobservedeffects:
Liquiddropletsformspheres
Meniscuseffectsincapillaries
SurfaceEnergyandTensioninLiquids
Thecohesiveforcesbetweenmolecules
downintoaliquidaresharedwithall
neighboringatoms.
Thoseonthesurfacehaveno
neighboringatomsabove,andexhibit
strongerattractiveforcesupontheir
nearestneighborsonthesurface.
Thisenhancementofthe
intermolecularattractiveforcesatthe
surfaceiscalledsurfacetension.
SurfaceTension:IntermolecularForces
SurfaceEnergyandTensioninLiquids
Inordertodevelopsomeconceptsrelatedtosurfaceswewillfirstlookatthesurface
propertiesofliquids.
Thework(w)requiredtocreateanewsurfaceisproportionaltothe#moleculesatthe
surface,hencethearea(A):
Where istheproportionalityconstantdefinedasthespecificsurfacefreeenergy.Ithas
unitsof(energy/unitarea,mJ/m
2
).
actsasarestoringforcetoresistanyincreaseinarea,forliquidsitisnumericallyequal
tothesurfacetension.
Whenconsideredasaforceratherthananenergy,theforceiscalled"surfacetensionand
hasunitsof(force/unitlength,mN/m)
A W o o =
1) Butt,HJ.;Graf,K.;Kappl PhysicsandChemistryofInterfaces,2
nd
Edition(WiletVCH:Weinheim 2006).
SurfaceEnergyandTensioninLiquids
actsasarestoringforcetoresistanyincreaseinarea,forliquidsitisnumericallyequal
tothesurfacetension.
Surfacetensioncanalsobedefinedbytheforcerequiredtoholdthesliderinplaceandto
balancethesurfacetensionalforce
L
dx
W
F = =
o
2
1) Butt,HJ.;Graf,K.;Kappl PhysicsandChemistryofInterfaces,2
nd
Edition(WiletVCH:Weinheim 2006).
SurfaceTensionofSolids
Bottomline:
Thesurfacetensionofsolidsisexperimentallyinaccessible.
Why?
Creationofnewareainasolidisnotreversible youendupstretchingorcleavingthe
sample.Interfacialstressduringelasticenlargementcanbemeasuredandrelatedto
interfacialtensiononlyiftherelationshipofinterfacialtensionasafunctionofstrainis
independentlyknown.
SurfaceTensionofExampleMaterials
Trends:
high materials(>200dyn/cm) metals,carbides,oxides
Low materials:polymersandorganics
Examples:SurfaceTensionofLiquidsinContact
withAir
TheYoungLaplaceEquation
Inphysics,theYoungLaplaceequationisanonlinearpartialdifferentialequation
thatdescribesthecapillarypressuredifferencesustainedacrosstheinterface
betweentwostaticfluids,suchaswaterandair,duetothephenomenonofsurface
tension.
fortheradiusofcurvatureindirections1(R
1
)and2(R
2
).Hence isbalancedby
AP,orthesurfacetensiontendstocompressthedroplet,increasingtheinternal
pressure.
Aninterestingconsequence:
|
|
.
|

\
|
+ = A
2 1
1 1
R R
P
p forwaterdropsofdifferentradiiatSTP
Dropletradius 1mm 0.1 mm 1m 10nm
p (atm) 0.0014 0.0144 1.436 143.6
Thepressuredifference(AP )acrossthe
surfaceofaliquidisrelatedtothesurface
curvature:
1) Butt,HJ.;Graf,K.;Kappl PhysicsandChemistryofInterfaces,2
nd
Edition(WiletVCH:Weinheim 2006).
TheYoungLaplaceEquation
Inasufficientlynarrow(i.e.,lowBondnumber)tubeofcircularcross
section(radiusa),theinterfacebetweentwofluidsformsameniscusthat
isaportionofthesurfaceofaspherewithradiusR.Thepressurejump
acrossthissurfaceis:
R
P
2
= A
TheYoungLaplaceEquation
YoungLaplacehasseveralfundamentalimplications:
Ifweknowtheshapeofaliquidsurfaceweknowitscurvatureandwecan
calculatethepressuredifference
Intheabsenceofexternalfields,thepressureisthesameeverywherein
theliquid;otherwisetherewouldbeaflowofliquidtoregionsoflower
pressure.Thus,PisconstantandYoungLaplaceequationtellsusthatin
thiscasethesurfaceoftheliquidhasthesamecurvatureeverywhere
WiththehelpofYoungLaplaceequation,itispossibletocalculatethe
equlibrium shapeofaliquidsurface.Ifweknowthepressuredifference
andsomeboundaryconditions(volumeofliquidanditscontactline),then
wecancalculatethegeometryoftheliquidsurface
ApplicationstoBiomaterials
Consequenceforthealveolarnetworkduringbreathing
Presenceofpulmonarysurfactantslowersurfacetensionand
stabilizethesystemrelatedtorespiratorydistresssyndrome
MeasuringSurfaceEnergyofSolids
FractureMethod
Acrackisopenedupbyforcespullingtheedges
apart.
A"doublecantilever"forms.Theworkdonebythe
appliedforceisequaltothepotentialenergyofthe
"leafsprings"andthesurfaceenergy.Solvingforthe
surfaceenergy(eventually)gives:
MeasuringSurfaceEnergyofSolids
IndentationMethod
Withsmallspecimensanindentationmethodisused.
Adiamondpointisforcedintothesurfaceandmicrocracks
appearatthesharpedges.
Itcanbeshown(butnotinthiscourse)thatthesurface
energyisgivenby:
Measuringthelengths,a,andc,andtheindentingforce,F,
willgivethesurfaceenergy.
MeasuringSurfaceTensionofLiquids
WinhelmyPlateMethod
Athinplatethatisusedtomeasure
equilibriumsurfaceorinterfacialtensionat
anairliquidorliquidliquidinterface.
Theplateisorientedperpendiculartothe
interface,andtheforceexertedonitis
measured
L thewettedperimeter(2w+2d)ofthe
Wilhelmy plateandisthecontactangle
betweentheliquidphaseandtheplate
Theforceontheplateduetowettingis
measuredviaatensiometer ormicrobalance
Plateisusuallyplatinum(easytocleanina
flame)
O
=
cos l
F

1) Butt,HJ.;Graf,K.;Kappl PhysicsandChemistryofInterfaces,2
nd
Edition(WiletVCH:Weinheim 2006).
MeasuringSurfaceTensionofLiquids
PendantDropMethod
A dropofliquidissuspendedfromtheendofa
tubebysurfacetension.
Theforceduetosurfacetensionisproportional
tothelengthoftheboundarybetweenthe
liquidandthetube,withtheproportionality
constantusuallydenoted.Sincethelengthof
thisboundaryisthecircumferenceofthetube,
theforceduetosurfacetensionisgivenby:
Themassm ofthedrophangingfromtheend
ofthetubecanbefoundbyequatingtheforce
duetogravity(F
g
=mg)withthecomponentof
thesurfacetensionintheverticaldirection
(F

sin)givingtheformula
Whereistheangleofcontactwiththetube,
andg istheaccelerationduetogravity.
Thelimitofthisformula,asgoesto90,gives
themaximumweightofapendantdropfora
liquidwithagivensurfacetension,.
t

d F =
td mg =
1) Butt,HJ.;Graf,K.;Kappl PhysicsandChemistryofInterfaces,2
nd
Edition(WiletVCH:Weinheim 2006).
MeasuringSurfaceTension
OtherMethodsinclude:
DuNoy ringtensionmeter
BubblePressureMethod
SessileDropMethod
1) Butt,HJ.;Graf,K.;Kappl PhysicsandChemistryofInterfaces,2
nd
Edition(WiletVCH:Weinheim 2006).