BiomaterialsLecture1516 Surfaces:Chemisorption& Corrosion

Unlessotherwisenoted,sourceInformationforthefollowingslides: 1) B.Ratner,A.Hoffman,F.Schoen,andJ.Lemons:BiomaterialsScience, 2nd edition(SanDiego:ElsevierAcademicPress.2004). 2) Butt,HJ.;Graf,K.;Kappl PhysicsandChemistryofInterfaces,2nd Edition (WiletVCH:Weinheim 2006). 3) Modifiedfrom:Anne Mayes3.051J/20.340JMaterialsforBiomedical Application,MIT,http://ocw.mit.edu,

CorrosioninAqueousEnvironment

ElectricDoubleLayer
Electricaldoublelayer: Thestructureofcharge accumulationandchargeseparationthatalways occursattheinterfacewhenanelectrodeis immersedintoanelectrolytesolution. Theexcesschargeontheelectrodesurfaceis compensatedbyanaccumulationofexcessions oftheoppositechargeinthesolution. Theamountofchargeisafunctionofthe electrodepotential.Thisstructurebehaves essentiallyasacapacitor. Thereareseveraltheoreticalmodelsthatdescribe thestructureofthedoublelayer.Thethreemost commonlyusedonesaretheHelmholtzmodel, theGouyChapmanmodel,andtheGouy ChapmanSternmodel.

Inotherwords,thedoublelayerisformedinorderto neutralizethechargedsurfaceand,inturn,causesan electrokinetic potentialbetweenthesurfaceandany pointinthemassofthesuspendingliquid.This voltagedifferenceisontheorderofmillivoltsandis referredtoasthesurfacepotential.

Adsorptionphenomena

Galvaniccorrosion

Anodicdissolution

Cathodic protection

B.Ratner,A.Hoffman,F.Schoen,andJ.Lemons:BiomaterialsScience, 2ndedition(SanDiego:ElsevierAcademicPress.2004).433.

Less Reactive

More Reactive

Commonlyusedsurgicalalloyscontainhighlyreactivemetals(i.e.with highnegativeelectrodepotential)suchastitanium,aluminum,chromium Becauseofhighreactivity,thesemetalsreactwithO2toforman imperviousoxidelayerfirmlyadherenttothemetalsurface,i.e. passivationlayer!!

Themostcommontypeoffrettingiscausedbyvibration.Theprotective filmonthemetalsurfacesisremovedbytherubbingactionandexposes fresh,activemetaltothecorrosiveactionoftheatmosphere.

B.Ratner,A.Hoffman,F.Schoen,andJ.Lemons:BiomaterialsScience, 2ndedition(SanDiego:ElsevierAcademicPress.2004).436.

Summary:BasicPrinciplesofCorrosion
Intheory,corrosionresistancecanbepredictedfromstandard electrodepotentials(i.e.explainsnobilityofsomemetalsand considerablereactivityinothers,notmuchuseforprediction inalloys) Irrespectiveofstandardelectrodepotentials,thecorrosion resistanceofmanymaterialsisdeterminedbytheirabilityto becomepassivated byanoxidelayerthatprotectsthe underlyingmetal Corrosionprocessesinpracticeareinfluencesbyvariationin surfacemicrostructuralfeaturesandintheenvironmentthat disruptsthechargetransferequlibrium