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CorrosionofEmbeddedMetals
Corrosionofreinforcingsteelandotherembeddedmetalsis
theleadingcauseofdeteriorationinconcrete.Whensteel
corrodes,theresultingrustoccupiesagreatervolumethan
thesteel.Thisexpansioncreatestensilestressesinthe
concrete,whichcaneventuallycausecracking,
delamination,andspalling.
Steelcorrodesbecauseitisnotanaturallyoccurring
material.Rather,ironoreissmeltedandrefinedtoproduce
steel.Theproductionstepsthattransformironoreintosteeladdenergytothemetal.
Steel,likemostmetalsexceptgoldandplatinum,isthermodynamicallyunstableundernormal
atmosphericconditionsandwillreleaseenergyandrevertbacktoitsnaturalstateironoxide,or
rust.Thisprocessiscalledcorrosion.
Forcorrosiontooccur,theseelementsmustbepresent:
Theremustbeatleasttwometals(ortwolocationsonasinglemetal)atdifferentenergylevels
anelectrolyte
ametallicconnection
Inreinforcedconcrete,therebarmayhavemanyseparateareasatdifferentenergylevels.Concrete
actsastheelectrolyte,andthemetallicconnectionisprovidedbywireties,chairsupports,orthe
rebaritself.
Corrosionisanelectrochemicalprocessinvolvingtheflowofcharges(electronsandions).Atactive

sitesonthebar,calledanodes,ironatomsloseelectronsand
moveintothesurroundingconcreteasferrousions.Thisprocess
iscalledahalfcelloxidationreaction,ortheanodicreaction,and
isrepresentedas:
2Fe2Fe2++4e
Theelectronsremaininthebarandflowtositescalledcathodes,
wheretheycombinewithwaterandoxygenintheconcrete.The
reactionatthecathodeiscalledareductionreaction.Acommon
reductionreactionis:
2H2O+O2+4e4OH

Tomaintainelectricalneutrality,theferrousionsmigratethroughtheconcreteporewatertothese
cathodicsiteswheretheycombinetoformironhydroxides,orrust:
2Fe2++4OH2Fe(OH)
Thisinitialprecipitatedhydroxidetendstoreactfurtherwithoxygentoformhigheroxides.The
increasesinvolumeasthereactionproductsreactfurtherwithdissolvedoxygenleadstointernal
stresswithintheconcretethatmaybesufficienttocausecrackingandspallingoftheconcrete
cover.

Corrosionofembeddedmetalsinconcretecanbegreatlyreducedbyplacingcrackfreeconcrete
withlowpermeabilityandsufficientconcretecover.Lowpermeabilityconcretecanbeattainedby
decreasingthewatertocementitiousmaterialsratiooftheconcreteandtheuseofpozzolansand
slag.Pozzolansandslagalsoincreasetheconcreteresistivitythusreducingthecorrosionrateeven
afteritinitiates.ACI31811,BuildingCodeRequirementsforStructuralConcreteprovidesminimum
concretecoverrequirementsthatwillhelpprotecttheembeddedmetalsfromcorrosivematerials.
Additionalmeasurestomitigatecorrosionofsteelreinforcementinconcreteincludetheuseof
corrosioninhibitingadmixtures,coatingofreinforcement(forexample,withanepoxyresin),anduse
ofsealersandmembranesontheconcretesurface.Sealersandmembranes,ifused,havetobe
periodicallyreapplied.

ConcreteandthePassiveLayer
Althoughsteelsnaturaltendencyistoundergocorrosionreactions,thealkalineenvironmentof
concrete(pHof12to13)providessteelwithcorrosionprotection.AtthehighpH,athinoxidelayer
formsonthesteelandpreventsmetalatomsfromdissolving.Thispassivefilmdoesnotactually
stopcorrosionitreducesthecorrosionratetoaninsignificantlevel.Forsteelinconcrete,the
passivecorrosionrateistypically0.1mperyear.Withoutthepassivefilm,thesteelwouldcorrode
atratesatleast1,000timeshigher(ACI2222001).

Becauseofconcretesinherentprotection,
reinforcingsteeldoesnotcorrodeinthemajority
ofconcreteelementsandstructures.However,
corrosioncanoccurwhenthepassivelayeris
destroyed.Thedestructionofthepassivelayer
occurswhenthealkalinityoftheconcreteis
reducedorwhenthechlorideconcentrationin
concreteisincreasedtoacertainlevel.

TheRoleofChlorideIons
Exposureofreinforcedconcretetochlorideionsistheprimarycauseofprematurecorrosionofsteel
reinforcement.Theintrusionofchlorideions,presentindeicingsaltsandseawater,intoreinforced
concretecancausesteelcorrosionifoxygenandmoisturearealsoavailabletosustainthereaction.
Chloridesdissolvedinwatercanpermeatethroughsoundconcreteorreachthesteelthrough
cracks.Chloridecontainingadmixturescanalsocausecorrosion.
Noothercontaminantisdocumentedasextensivelyintheliteratureasacauseofcorrosionof
metalsinconcretethanchlorideions.Themechanismbywhichchloridespromotecorrosionisnot
entirelyunderstood,butthemostpopulartheoryisthatchlorideionspenetratetheprotectiveoxide
filmeasierthandootherions,leavingthesteelvulnerabletocorrosion.
Theriskofcorrosionincreasesasthechloridecontentof
concreteincreases.Whenthechloridecontentatthesurface
ofthesteelexceedsacertainlimit,calledthethreshold
value,corrosionwilloccurifwaterandoxygenarealso
available.FederalHighwayAdministration(FHWA)studies
foundthatathresholdlimitof0.20percenttotal(acid
soluble)chloridebyweightofcementcouldinducecorrosion
ofreinforcingsteelinbridgedecks(Clear1976).However,
onlywatersolublechloridespromotecorrosionsomeacid
solublechloridesmaybeboundwithinaggregatesand,therefore,unavailabletopromotecorrosion.

WorkattheFHWA(Clear1973)foundthattheconversionfactorfromacidsolubletowatersoluble
chloridescouldrangefrom0.35to0.90,dependingontheconstituentsandhistoryoftheconcrete.
Arbitrarily,0.75waschosen,resultinginawatersolublechloridelimitof0.15percentbyweightof
cement.
Althoughchloridesaredirectlyresponsiblefortheinitiationofcorrosion,theyappeartoplayonlyan
indirectroleintherateofcorrosionafterinitiation.Theprimaryratecontrollingfactorsarethe
availabilityofoxygen,theelectricalresistivityandrelativehumidityoftheconcrete,andthepHand
temperature.

Carbonation
Carbonationoccurswhencarbondioxidefromtheairpenetratestheconcreteandreactswith
hydroxides,suchascalciumhydroxide,toformcarbonates.Inthereactionwithcalciumhydroxide,
calciumcarbonateisformed:
Ca(OH)2+CO2CaCO3+H2O
ThisreactionreducesthepHoftheporesolutiontoaslowas8.5,atwhichlevelthepassivefilmon
thesteelisnotstable.
Carbonationisgenerallyaslowprocess.Inhighqualityconcrete,ithasbeenestimatedthat
carbonationwillproceedatarateupto0.04inchesperyear.Theamountofcarbonationis
significantlyincreasedinconcretewithahighwatertocementratio,lowcementcontent,short
curingperiod,lowstrength,andhighlypermeableorporouspaste.
Carbonationishighlydependentontherelativehumidityoftheconcrete.Thehighestratesof
carbonationoccurwhentherelativehumidityismaintainedbetween50and75percent.Below25
percentrelativehumidity,thedegreeofcarbonationthattakesplaceisconsideredinsignificant.
Above75percentrelativehumidity,moistureintheporesrestrictsCO2penetration.Carbonation
inducedcorrosionoftenoccursonareasofbuildingfacadesthatareexposedtorainfall,shaded
fromsunlight,andhavelowconcretecoveroverthereinforcingsteel.
Carbonationofconcretealsolowerstheamountofchlorideionsneededtopromotecorrosion.In
newconcretewithapHof12to13,about7,000to8,000ppmofchloridesarerequiredtostart
corrosionofembeddedsteel.If,however,thepHisloweredtoarangeof10to11,thechloride
thresholdforcorrosionissignificantlyloweratorbelow100partspermillion.Likechlorideions,
however,carbonationdestroysthepassivefilmofthereinforcement,butdoesnotinfluencetherate
ofcorrosion.

Exampleofcarbonationonabuildingfacade.

DissimilarMetalCorrosion
Whentwodifferentmetals,suchasaluminumandsteel,areincontactwithinconcrete,corrosion
canoccurbecauseeachmetalhasauniqueelectrochemicalpotential.Afamiliartypeofdissimilar
metalcorrosionoccursinanordinaryflashlightbattery.Thezinccaseandcarbonrodarethetwo
metals,andthemoistpasteactsastheelectrolyte.Whenthecarbonandzincareconnectedbya
wire,currentflows.Inreinforcedconcrete,dissimilarmetalcorrosioncanoccurinbalconieswhere
embeddedaluminumrailingsareincontactwiththereinforcingsteel.Belowisalistofmetalsin
orderofelectrochemicalactivity:

1.Zinc5.Nickel9.Copper
2.Aluminum6.Tin10.Bronze
3.Steel7.Lead11.StainlessSteel

4.Iron8.Brass12.Gold
Whenthemetalsareincontactinanactiveelectrolyte,thelessactivemetal(lowernumber)inthe
seriescorrodes.

References
ACICommittee222,ProtectionofMetalsinConcreteAgainstCorrosion,ACI222R01,American
ConcreteInstitute,FarmingtonHills,Michigan,2001,41pages.

ACICommittee318,BuildingCodeRequirementsforStructuralConcrete,ACI31805,American
ConcreteInstitute,FarmingtonHills,Michigan,2005,443pages.
Clear,K.C.,andHay,R.E.,TimetoCorrosionofReinforcingSteelinConcreteSlabe,V.1:Effectof
MixDesignandConstructionParameters,FHWARD7332,FederalHighwayAdministration,
Washington,DC,April,1973,103pages.
ClearK.C.,TimetoCorrosionofReinforcingSteelinConcreteSlabs,FederalHighway
Administration,PB258446,Vol.3,April,1976.
PCA,TypesandCausesofConcreteDeterioration,PortlandCementAssociation,Skokie,Illinois,
2002,16pages.

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