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GettingStartedwithElectrochemicalCorrosionMeasurement
ReviewoftheElectrochemicalBasisofCorrosion
Mostmetalliccorrosionoccursviaelectrochemicalreactionsattheinterfacebetweenthemetalandanelectrolytesolution.Forexample,athinfilmofmoistureonametalsurface
formstheelectrolyteforatmosphericcorrosion.Asecondexampleiswhenwetconcreteistheelectrolyteforreinforcingrodcorrosioninbridges.Althoughmostcorrosiontakesplacein
water,corrosioninnonaqueoussystemsisnotunknown.
Corrosionnormallyoccursataratedeterminedbyanequilibriumbetweenopposingelectrochemicalreactions.Onereactionistheanodicreaction,inwhichametalisoxidized,releasing
electronsintothemetal.Theotheristhecathodicreaction,inwhichasolutionspecies(oftenO2orH+)isreduced,removingelectronsfromthemetal.Whenthesetworeactionsarein
equilibrium,theflowofelectronsfromeachreactionisbalanced,andnonetelectronflow(electricalcurrent)occurs.Thetworeactionscantakeplaceononemetalorontwodissimilar
metals(ormetalsites)thatareelectricallyconnected.
Figure1sketchesthisprocess.Theverticalaxisiselectricalpotentialandthehorizontalaxisisthelogarithmofabsolutecurrent.Thetheoreticalcurrentfortheanodicandcathodic
reactionsisrepresentedasstraightlines.Thecurvedlineisthetotalcurrent:thesumoftheanodicandcathodiccurrents.Thisisthecurrentthatyoumeasurewhenyousweepthe
potentialofthemetalwithyourpotentiostat.Thesharppointinthecurveisactuallythepointwherethecurrentreversespolarityasthereactionchangesfromanodictocathodic,or
viceversa.Thesharppointiscausedbyplottingalongalogarithmicaxis.Theuseofalogarithmicaxisisnecessarybecauseofthewiderangeofcurrentvaluesthatmustberecorded
duringacorrosionexperiment.Becauseofthephenomenonofpassivity,thecurrentoftenchangebysixordersofmagnitudeduringacorrosionexperiment.

Figure1.Corrosionprocessshowinganodicandcathodiccomponentsofcurrent.
Thepotentialofthemetalisthemeansbywhichtheanodicandcathodicreactionsarekeptinbalance.RefertoFigure1.Noticethatthecurrentfromeachhalfreactiondependson
theelectrochemicalpotentialofthemetal.Supposethattheanodicreactionreleasestoomanyelectronsintothemetal.Excesselectronsthusshiftthepotentialofthemetalmore
negative,whichslowstheanodicreactionandspeedsupthecathodicreaction.Thiscounteractstheinitialperturbationofthesystem.
Theequilibriumpotentialassumedbythemetalintheabsenceofelectricalconnectionstothemetaliscalledtheopencircuitpotential,E oc.Inmostelectrochemicalcorrosion
experiments,thefirststepisthemeasurementofE oc.
ThevalueofeithertheanodicorcathodiccurrentatE ociscalledthecorrosioncurrent,Icorr.IfwecouldmeasureIcorr,wecoulduseittocalculatethecorrosionrateofthemetal.
Unfortunately,Icorrcannotbemeasureddirectly.However,itcanbeestimatedusingelectrochemicaltechniques.Inanyrealsystem,Icorrandcorrosionrateareafunctionofmany
systemparameters,includingtypeofmetal,compositionofthesolution,temperature,movementofthesolution,metalhistory,andmanyothers.
Theabovedescriptionofthecorrosionprocessdoesnotsayanythingaboutthestateofthemetalsurface.Inpractice,manymetalsformanoxidelayerontheirsurfaceasthey
corrode.Iftheoxidelayerinhibitsfurthercorrosion,themetalissaidtopassivate.Insomecases,localareasofthepassivefilmbreakdown,allowingsignificantmetalcorrosionto
occurinasmallarea.Thisphenomenoniscalledpittingcorrosionorsimplypitting.
Becausecorrosionoccursviaelectrochemicalreactions,electrochemicaltechniquesareidealforthestudyofthecorrosionprocesses.Inelectrochemicalstudies,ametalsamplewitha
surfaceareaofafewsquarecentimetersisusedtomodelthemetalinacorrodingsystem.Themetalsampleisimmersedinasolutiontypicalofthemetalsenvironmentinthesystem
beingstudied.Additionalelectrodesareimmersedinthesolution,andalltheelectrodesareconnectedtoadevicecalledapotentiostat.Apotentiostatallowsyoutochangethe
potentialofthemetalsampleinacontrolledmannerandmeasurethecurrentthatflowsasafunctionofappliedpotential.
Bothcontrolledpotential(potentiostatic)andcontrolledcurrent(galvanostatic)polarizationareuseful.Whenthepolarizationisdonepotentiostatically,currentismeasured,andwhen
itisdonegalvanostatically,potentialismeasured.Thisdiscussionwillconcentrateoncontrolledpotentialmethods,whicharemuchmorecommonthangalvanostaticmethods.With
theexceptionofopencircuitpotentialversustime,electrochemicalnoise,galvaniccorrosion,andafewothers,potentiostaticmodeisusedtoperturbtheequilibriumcorrosionprocess.
WhenthepotentialofametalsampleinsolutionisforcedawayfromE oc,itisreferredtoaspolarizingthesample.Theresponse(thatis,resultingcurrent)ofthemetalsampleis
measuredasitispolarized.Theresponseisusedtodevelopamodelofthesamplescorrosionbehavior.

QuantitativeCorrosionTheory
IntheprevioussectionwepointedoutthatIcorrcannotbemeasureddirectly.Inmanycases,youcanestimateitfromcurrentversusvoltagedata.Youcanmeasurealogarithmic
currentversuspotentialcurveoverarangeofaboutonehalfvolt.ThevoltagescaniscenteredonE oc.Youthenfitthemeasureddatatoatheoreticalmodelofthecorrosionprocess.
Themodelweuseforthecorrosionprocessassumesthattheratesofboththeanodicandcathodicprocessesarecontrolledbythekineticsoftheelectrontransferreactionatthe
metalsurface.Thisisgenerallythecaseforcorrosionreactions.AnelectrochemicalreactionunderkineticcontrolobeysEq.1,theTafelequation.

Inthisequation,

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I isthecurrentresultingfromthereaction
I0 isareactiondependentconstantcalledtheexchangecurrent
E istheelectrodepotential
E 0istheequilibriumpotential(constantforagivenreaction)
isthereactionsTafelconstant(constantforagivenreaction,withunitsofvolts/decade.
TheTafelequationdescribesthebehaviorofoneisolatedreaction.Inacorrosionsystem,wehavetwoopposingreactions:anodicandcathodic.
TheTafelequationsfortheanodicandcathodicreactionsinacorrosionsystemcanbecombinedtogeneratetheButlerVolmerequation(Eq.2).

where
I

isthemeasuredcurrentfromthecellinampres

Icorr isthecorrosioncurrentinampres
E

istheelectrodepotential

E corristhecorrosionpotentialinvolts
a

istheanodicTafelconstantinvolts/decade

isthecathodicTafelconstantinvolts/decade

WhatdoesEq.2predictaboutthecurrentversusvoltagecurve?AtE corr,eachexponentialtermequalsone.Thecellcurrentisthereforezero,asyouwouldexpect.NearE corr,both

exponentialtermscontributetotheoverallcurrent.Finally,asthepotentialisdrivenfarfromE corrbythepotentiostat,oneexponentialtermpredominatesandtheothertermcanbe
ignored.Whenthisoccurs,aplotoflogarithmiccurrentversuspotentialbecomesastraightline.
AplotoflogIversusEiscalledaTafelplot.TheTafelplotinFigure1wasgenerateddirectlyfromtheButlerVolmerequation.Noticethelinearsectionsofthecellcurrentcurve.
Inpractice,manycorrosionsystemsarekineticallycontrolledandthusobeyEq.2.AcurveoflogarithmiccurrentversuspotentialthatislinearonbothsidesofE corrisindicativeof
kineticcontrolforthesystembeingstudied.However,therecanbecomplications,suchas:
Concentrationpolarization,wheretherateofareactioniscontrolledbytherateatwhichreactantsarriveatthemetalsurface.Oftencathodicreactionsshowconcentration
polarizationathighercurrents,whendiffusionofoxygenorhydrogenionisnotfastenoughtosustainthekineticallycontrolledrate.
Oxideformation,whichmayormaynotleadtopassivation.Thisprocesscanalterthesurfaceofthesamplebeingtested.Theoriginalsurfaceandthealteredsurfacemayhave
differentvaluesfortheconstantsinEq.2.
Othereffectsthatalterthesurface,suchaspreferentialdissolutionofonecomponentofanalloy,canalsocauseproblems.
Amixedcontrolprocesswheremorethanonecathodic,oranodic,reactionoccurssimultaneouslymaycomplicatethemodel.Anexampleofmixedcontrolisthesimultaneous
reductionofoxygenandhydrogenion.
Finally,potentialdropasaresultofcellcurrentflowingthroughtheresistanceofyourcellsolutioncauseserrorsinthekineticmodel.Thislasteffect,ifitisnottoosevere,maybe
correctableviaIRcompensationinthepotentiostat.
Inmostcases,complicationslikethoselistedabovecausenonlinearitiesintheTafelplot.UsewithcautiontheresultsderivedfromaTafelplotwithoutawelldefinedlinearregion.
ClassicTafelanalysisisperformedbyextrapolatingthelinearportionsofalogarithmiccurrentversuspotentialplotbacktotheirintersection.SeeFigure2(whichisFigure1reprinted
withannotationsthatdemonstratetheanalysis).ThevalueofeithertheanodicorthecathodiccurrentattheintersectionisIcorr.Unfortunately,manyrealworldcorrosionsystemsdo
notprovideasufficientlinearregiontopermitaccurateextrapolation.Mostmodern
corrosiontestsoftware,suchasGamryInstrumentsDC105DCCorrosionTechniquessoftware,performsamoresophisticatednumericalfittotheButlerVolmerequation.The
measureddataarefittoEq.2byadjustingthevaluesofE corr,Icorr,a,andc.Thecurvefittingmethodhastheadvantagethatitdoesnotrequireafullydevelopedlinearportionof
thecurve.

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Figure2.ClassicTafelanalysis.

PolarizationResistance
Eq.2canbefurthersimplifiedbyrestrictingthepotentialtobeveryneartoE corr.ClosetoE corr,thecurrentversusvoltagecurveapproximatesastraightline.Theslopeofthislinehas
theunitsofresistance().Theslopeis,therefore,calledthepolarizationresistance,Rp.AnRpvaluecanbecombinedwithanestimateofthecoefficientstoyieldanestimateofthe
corrosioncurrent.
IfweapproximatetheexponentialtermsinEq.2withthefirsttwotermsofapowerseriesexpansion()andsimplify,wegetoneformoftheSternGearyequation:

Inapolarizationresistanceexperiment,yourecordacurveofcurrentversusvoltageasthecellvoltageissweptoverasmallrangeofpotentialthatisveryneartoE oc(generally10
mV).Anumericalfitofthecurveyieldsavalueforthepolarizationresistance,Rp.Polarizationresistancedatadonotprovideanyinformationaboutthevaluesforthecoefficients.
Therefore,touseEq.3,youmustprovidevalues.ThesecanbeobtainedfromaTafelplot,orestimatedfromyourexperiencewiththesystemyouaretesting.

CalculationofCorrosionRatefromCorrosionCurrent
Thenumericalresultobtainedbyfittingcorrosiondatatoamodelisgenerallythecorrosioncurrent.Weareinterestedincorrosionratesinthemoreusefulunitsofrateofpenetration,
suchasmillimetersperyear.Howiscorrosioncurrentusedtogenerateacorrosionrate?Assumeanelectrolyticdissolutionreactioninvolvingachemicalspecies,S:
SS n++n e
YoucanrelatecurrentflowtomassviaFaradaysLaw.
Q=nFMEq.4
where
QisthechargeincoulombsresultingfromthereactionofspeciesS
n isthenumberofelectronstransferredpermoleculeoratomofS
F isFaradaysconstant=96485coulombs/mole
MisthenumberofmolesofspeciesSreacting
AmoreusefulformofEq.4requirestheconceptofequivalentweight.Theequivalentweight(EW)isthemassofspeciesSthatwillreactwithoneFaradayofcharge.Foranatomic
species,EW=AW/n(whereAWistheatomicweightofthespecies).
RecallingthatM=m/AWandsubstitutingintoEq.4weget:

wheremisthemassofspeciesSthathasreacted.
Incaseswherethecorrosionoccursuniformlyacrossametalsurface,thecorrosionratecanbecalculatedinunitsofdistanceperyear.Becareful:thiscalculationisonlyvalidfor
uniformcorrosionitdramaticallyunderestimatestheproblemwhenlocalizedcorrosionoccurs!
Foracomplexalloythatundergoesuniformdissolution,theequivalentweightisaweightedaverageoftheequivalentweightsofthealloycomponents.Molefraction,notmassfraction,
isusedastheweightingfactor.Ifthedissolutionisnotuniform,youmayhavetomeasurethecorrosionproductstocalculateEW.
Conversionfromaweightlosstoacorrosionrate(CR)isstraightforward.Weneedtoknowthedensity,d,andthesamplearea,A.ChargeisgivenbyQ=It,wheretisthetimein
secondsandIisacurrent.WecansubstituteinthevalueofFaradaysconstant.ModifyingEq.5,

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where
IcorrThecorrosioncurrentinampres
K

Aconstantthatdefinestheunitsforthecorrosionrate

EW Theequivalentweightingrams/equivalent
d

Densitying/cm3

Sampleareaincm2

Table1.CorrosionRateConstants
UnitsforcorrosionrateK

Units

mm/year(mmpy)

mm(Acmyear)

3272

milliinches/year(mpy)1.28810 5milliinches(Acmyear)

IRCompensation
Whenyoupasscurrentbetweentwoelectrodesinaconductivesolution,therearealwaysregionsofdifferentpotentialsinthesolution.Muchoftheoverallchangeinpotentialoccurs
veryclosetothesurfaceoftheelectrodes.Herethepotentialgradientsarelargelycausedbyionicconcentrationgradientssetupnearthemetalsurfaces.Also,thereisalwaysa
potentialdifference(apotentialdrop)causedbycurrentflowthroughtheresistanceinthebulkofthesolution.
Inanelectrochemicalexperiment,thepotentialthatyouwishtocontrolormeasureisthepotentialofametalspecimen(calledtheWorkingElectrode)versusaReferenceElectrode.
Wearenormallynotinterestedinthepotentialdropscausedbysolutionresistancesbecausetheyarenegligibleintypicalelectrolytesolutionssuchas1MH2SO4or5%NaCl.
GamryInstrumentspotentiostats,likeallmodernelectrochemicalinstruments,arethreeelectrodepotentiostats.Theymeasureandcontrolthepotentialdifferencebetweenanon
currentcarryingReferenceElectrodeandoneofthetwocurrentcarryingelectrodes(theWorkingElectrode).Thepotentialdropneartheothercurrentcarryingelectrode(theCounter
Electrode)doesnotmatterwhenathreeelectrodepotentiostatisused.
CarefulplacementoftheReferenceElectrodecancompensateforsomeoftheIRdropresultingfromthecellcurrent,I,flowingthroughthesolutionresistance,R.Youcanthinkofthe
ReferenceElectrodeassamplingthepotentialsomewherealongthesolutionresistance.ThecloseritistotheWorkingElectrode,thecloseryouaretomeasuringapotentialfreefrom
IRerrors.However,completeIRcompensationcannotbeachievedinpracticethroughplacementofthereferenceelectrode,becauseofthefinitephysicalsizeoftheelectrode.The
portionofthecellresistancethatremainsafterplacingtheReferenceElectrodeiscalledtheuncompensatedresistance,Ru.
GamrypotentiostatscanusecurrentinterruptorpositivefeedbackIRcompensationtodynamicallycorrectuncompensatedresistanceerrors.Inthecurrentinterrupttechnique,the
cellcurrentisperiodicallyturnedoffforaveryshorttime.Withnocurrentflowingthroughthesolutionresistance,itsIRdropdisappearsinstantly.Thepotentialdropattheelectrode
surfaceremainsconstantonarapidtimescale.ThedifferenceinpotentialwiththecurrentflowingandwithoutisameasureoftheuncompensatedIRdrop.
Thepotentiostatmakesacurrentinterruptmeasurementimmediatelyafteritacquireseachdatapoint.Thepotentiostatactuallytakesthreepotentialreadings:E 1beforethecurrent
isturnedoff,andE 2andE 3whileitisoff(seeFigure3).Normally,thelattertwoareusedtoextrapolatethepotentialdifference,E,backtotheexactmomentwhenthecurrentwas
interrupted.Thetimingoftheinterruptdependsonthecellcurrent.Theinterrupttimeis40sonthehighercurrentranges.Onlowercurrentranges,theinterruptlastslonger.

Figure3.Currentinterruptpotentialversustime.
Incontrolledpotentialmodes,theappliedpotentialcanbedynamicallycorrectedforthemeasuredIRerrorinoneofseveralways.Inthesimplestofthese,theIRerrorfromthe
previouspointisappliedasacorrectiontotheappliedpotential.Forexample,ifanIRfreepotentialof1Visdesired,andthemeasuredIRerroris0.2V,thepotentiostatapplies1.2V.
Thecorrectionisalwaysonepointbehind,fortheIRerrorfromonepointisappliedtocorrecttheappliedpotentialforthenextpoint.Inadditiontothisnormalmode,aGamry
Instrumentspotentiostatoffersmorecomplexfeedbackmodesinwhichthetwopointsonthedecaycurveareaveraged.

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Bydefaultinthecontrolledpotentialmodes,thepotentialerrormeasuredviacurrentinterruptisusedtocorrecttheappliedpotential.Inthecontrolledcurrentmodes,nocorrectionis
required.IfIRcompensationisselected,themeasuredIRerrorissubtractedfromthemeasuredpotential.AllreportedpotentialsarethereforefreefromIRerror.
Foradetailedtheoreticaldiscussionofuncompensatedresistance,seeKeithB.Oldham,etal.,AnalyticalChemistry,72(2000),3972and3981.

CurrentandVoltageConventions
Currentpolaritiesinelectrochemicalmeasurementscanbeinconsistent.Acurrentvalueof1.2mAcanmeandifferentthingstoworkersindifferentbranchesofelectrochemistryorin
differentcountriesoreventodifferentpotentiostats.Toananalyticalelectrochemistitrepresents1.2mAofanodiccurrent.Toacorrosionscientistitrepresents1.2mAofcathodic
current.AGamryInstrumentspotentiostatindefaultmodefollowsthecorrosionconventionforcurrentinwhichpositivecurrentsareanodicandnegativecurrentsarecathodic.For
theconvenienceofourusersaroundtheworld,GamryInstrumentspotentiostatscanprovidethecurrentpolarityasperyourpreferencewithasimplesoftwarecommand.
Thepolarityofthepotentialcanalsobeasourceofconfusion.Inelectrochemicalcorrosionmeasurement,theequilibriumpotentialassumedbythemetalintheabsenceofelectrical
connectionstothemetaliscalledtheopencircuitpotential,E oc.Weusethetermcorrosionpotential,E corr,forthepotentialinanelectrochemicalexperimentatwhichnocurrent
flows,asdeterminedbyanumericalfitofcurrentversuspotentialdata.Inanidealcase,thevaluesforE ocandE corrareidentical.Onereasonthetwovoltagesmaydifferisthat
changeshaveoccurredtotheelectrodesurfaceduringthescan.
Withmostmodernpotentiostats,allpotentialsarespecifiedorreportedasthepotentialoftheworkingelectrodewithrespecttoeitherthereferenceelectrodeortheopencircuit
potential.Theformerisalwayslabeledasvs.E ref andthelatterasvs.E oc.Theequationstoconvertfromoneformofpotentialtotheotherare:
Evs.Eoc=(Evs.Eref)Eoc
Evs.Eref=(Evs.Eoc)+Eoc
RegardlessofwhetherpotentialsareversusE ref orversusE oc,onesignconventionisused.Themorepositiveapotential,themoreanodicitis.Moreanodicpotentialsaccelerate
oxidationattheWorkingElectrode.Conversely,anegativepotentialacceleratesreductionattheWorkingElectrode.

SomeReferencesonCorrosionTheoryandElectrochemicalCorrosionTests
DCElectrochemicalTestMethods,N.G.ThompsonandJ.H.Payer,NationalAssociationofCorrosionEngineers.ISBN:1877914630.
PrinciplesandPreventionofCorrosion,DennyA.Jones,PrenticeHall,1996.ISBN0133599930.
PolarizationResistanceMethodforDeterminationofInstantaneousCorrosionRates,J.R.Scully,Corrosion,56(2000),199.
SeveralelectrochemicalcorrosiontechniquesareapprovedbytheASTM(AmericanSocietyforTestingandMaterials,100BarrHarborDrive,WestConshohocken,PA19428.Theymay
befoundinVolume3.02oftheASTMStandards:
G5:PotentiostaticandPotentiodynamicAnodicPolarizationMeasurements
G59:PolarizationResistanceMeasurements
G61:CyclicPolarizationMeasurementsforLocalizedCorrosionSusceptibilityofIron,Nickel,andCobaltBasedAlloys
G100:CyclicGalvanostaircasePolarization
G106:VerificationofAlgorithmandEquipmentforElectrochemicalImpedanceMeasurements
G108:ElectrochemicalPotentiokineticReactivation(EPR)forDetectingSensitization
G150:ElectrochemicalCriticalPittingTemperatureTestingofStainlessSteels
ElectrochemicalTechniquesinCorrosionEngineering,NationalAssociationofCorrosionEngineers,1986.
CorrosionTestingandEvaluation,STP1000,Ed.R.BaboianandS.W.Dean,AmericanSocietyforTestingandMaterials,WestConshohocken,PA,1991.ISBN0803114060.
ElectrochemicalCorrosionTesting,STP727,Ed.F.MansfeldandU.Bertocci,AmericanSocietyforTestingandMaterials,WestConshohocken,PA,1979.
CorrosionandCorrosionControl,3rded.,HerbertH.Uhlig,JohnWileyandSons,NewYork,1985.

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