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Engineer'sGuidetoCorrosion:Part1|Engineering360

DesignandAnalysis

Engineer'sGuideto
Corrosion:Part1
BradBuecker,ProcessSpecialist,KiewitEngineeringandDesignCo.
25September2016

Engineersandprofessionalstaffatindustrialplantsknowthatraw,
intermediate,andfinalproductsmaybehighlycorrosivetoplant
piping,heatexchangers,vessels,andotherequipment,aswellasto
people.
However,corrosioncanbejustasseriousonthewater/steamsideof
theplant.Inaseriesofarticleswewillexaminesomeofthemost
importantaspectsofcorrosionthatarerelatedtowaterandsteam
useinindustrialplantsandpowergenerationfacilities.
Theprimarymetalsthatwewillexamine,especiallyinlaterpartsof
theseries,arecarbonsteel,stainlesssteels,andcopperalloys.We
beginbyoutliningthemostcommoncorrosionmechanisms.
CorrosionFundamentals
Corrosionofmetalsalwaysinvolvesanelectrochemicalprocess.But
inthecaseoferosioncorrosion,mechanicalinfluencesarealso
present.Althoughmanydifferenttypesofcorrosionhavebeen
discovered(andsomehavenotyetbeencompletelyinvestigated),
thefollowingexampleillustratesthefundamentalconceptsof
corrosion.
Considerasimplelaboratoryexperimentofimmersinganironbarin
ahydrochloricacid(HCl)solution.Afterafewdays,corrosionspots
willbecomeplainlyvisibleonthebar.Thefigureillustratesthe
corrosionmechanism.
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Threestepsexplainthebasic
process:
1.Eachironatomatthecorrosion
sitegivesuptwoelectrons
(oxidizes),andthustransforms
fromazerooxidationstatetoa+2
oxidationstate,
(Clicktoenlarge.)Basiccorrosioncell.
Source:Author'sconstruct.

(Eq.1.)

TheFe+2(ferrous)
ionsmigrateintothesolution.Thissiteisknownastheanode.
2.Theelectronsflowthroughthemetaltoanothersitewherethey
reactwiththehydrogenionsoftheacid(reduction)toproduce
hydrogengas,
(Eq.2.)
Thisreactionoccursatthecathode.
3.Theanionsfromtheacid,chlorideions(Cl),andtheferrousions
migratethroughsolutiontoproducesolvatedferrouschloride
(FeCl2).Whatisevidentfromthisexampleisthatanelectricalcircuit
iscompleted.Withoutthiselectricalcircuit,corrosiondoesnotoccur.
Anotherfundamentalcathodicreaction,andonethatgreatly
influenceswatertreatmentis,
(Eq.3.)
Thisisthetypicalcathodicreactioninwater
containingdissolvedoxygen.Thehydroxylionscombinewithironto
formferroushydroxide,[Fe(OH)2],whichfurtheroxidestoferric
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Engineer'sGuidetoCorrosion:Part1|Engineering360

hydroxideprecipitate[Fe(OH)3].Dehydrolysisofferrichydroxide
producesFe2O3,whichwecommonlyknowasrust.
Manytypesofcorrosionareknown.Some,however,aremore
commonthanothers.Elevenofthemostimportantcorrosion
mechanismsconcerningwater/steamusearegeneralcorrosion,
pitting,crevicecorrosion,galvaniccorrosion,erosioncorrosion
(particularlyflowacceleratedcorrosion),stresscorrosioncracking,
corrosionfatigue,intergranularcorrosion,dealloying,exfoliation,and
microbiologicallyinfluencedcorrosion.
Thefollowingsectionsoutlinethesemechanisms.
GeneralCorrosion:Generalcorrosionoccurswhenametalis
attackeduniformlybyacorrodingsubstance.Thecorrosionofactive
metalsbyacidisaprimeexample.Pipes,tubes,andotherpower
plantmaterialsarealwaysdesignedwithageneralcorrosionsafety
factor.Sincegeneralcorrosionisspreadoverawidearea,metal
integritymayremainsolidformanyyears.Unfortunately,many
corrosionmechanismsarenotgeneralinnaturebutarelocalized.
Thesearemuchmoreserious.
Pitting:Pittingisalocalizedformofattackinwhichthecorrosion
penetratesdownandthroughthemetal.Pittingisaninsidious
mechanismandmaycausefailuresevenwhenthebulkofthe
materialisstillingoodshape.
Severaltypesofpittingarepossible.Oneofthemostcommonis
underdepositcorrosion,whichisaphenomenonthatoccursin
boilersandcoolingwatersystems.Depositsincoolingwatersystems
generateoxygendifferentialcells,inwhichtheenvironment
underneaththedepositbecomesoxygendeficientincomparisonto
thebulksolution.Thiscausesthetubemetalbelowthedepositto
becomeanodictocleansurfaces,whereoxygenisingoodsupply.
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Diagramshowingamechanismof
localizedcorrosiondevelopingonmetalin
asolutioncontainingoxygen.Image
source:Wikipedia

Underdepositcorrosionisone
oftheprimaryreasonswhyitis
soimportanttopreventfouling
andscalinginwatersystems.
Depositsinboilersmay
produceoxygendifferential
cells,ortheymaytrapcorrosive
materialsunderneaththat
attacktheboilertubesdirectly.

Anotherformofpittingisan
attackcommontostainlesssteels.Stainlesssteelsdevelopanoxide
surfacelayerthatprotectsthebasemetal.Thisoxidelayermaybe
penetratedbyimpuritiesinthewater.Chlorideisaparticularly
notoriouspittingagent,anditwillattacksomegradesofstainless
steel,includingoneofthemostcommonlyusedheatexchanger
materials,304stainless.Astheattackcontinues,thechloride
concentrationinthepitincreasesandthepHgoesdown,further
exacerbatingtheproblem.
Rememberthatalthoughstainlesssteelsarewidelyusedthroughout
thepower,chemical,andmanufacturingindustriesforpiping,
vessels,heatexchangers,andotherequipment,somepeople
assumethatstainlessmaterialsarebulletproof.Thisisamyth.If
stainlesssteelsareselectedimproperlyorforthewrongapplication,
corrosionfailurescanoccurrapidly.
CreviceCorrosion:Crevicecorrosionalmostcanbethoughtofas
pitting,butinthiscaseamechanicalfactor,namelythephysical
joiningtogetheroftwometals,leadstosites(crevices)thatbecome
oxygendepleted.Thesesitesbecomeanodictotheexposedmetal
surfaceandcorrodeinasimilarmechanismtotheunderdeposit
process.

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GalvanicCorrosion:Galvaniccorrosionoccurswhentwodissimilar
metalsarecoupledtogetherinacorrosivemedium.Themore
passiveofthetwoservesasacathodeandthemorereactive
becomesananode.Galvaniccorrosioncanbeespeciallysevere
whenasmallanodeiscoupledwithalargecathode.Oneclassic
exampleisofcopperplatesthatareconnectedbysteelrivetsin
seawaterservice.Corrosionoftherivetscanbeintense.Thereverse
situation,namelycopperrivetsholdingsteelplates,isbetterfroma
corrosionstandpoint,asalargeanodeiscoupledtoasmallcathode.
Althoughcorrosionofthesteelstilloccurs,metallossislesssevere.
ErosionCorrosion:Erosioncorrosionisacombinationofphysical
andchemicalattack.Itoccurswhenaflowingstreamerodesthe
outerlayerofthemetalexposingfreshmetaltofurthercorrosion.
Highfluidvelocityordisturbancesinflowpatternsmayinitiate
erosioncorrosion.Aspecialformoferosioncorrosion,flow
acceleratedcorrosion(FAC),hascausedgreatconcerninthepower
industry.
StressCorrosionCracking:Stresscorrosioncracking(SCC)is
anothermechanical/chemicalmechanism.Thecorrosionoccursat
stresspointsinmetals,whichareattackedbyaspecificagent.The
304and316stainlesssteelsofferagoodexample.Whenplaced
understressinacorrosiveenvironment,suchasasolution
containingchlorides,thematerialwillbegintocorrodeatthestress
points.TurbinebladesareprimelocationsforSCC,astheyare
constantlyunderstress.
FatigueandCorrosionFatigue:Breakingawirebybendingitback
andforthrepeatedlyuntilitfailsisanexampleoffatigueinwhich
failurewascausedbycyclicalstress.Fatiguerelatedfailuresoccur
commonlyatsupportlocationsinboilerswhere,asthetubesheator
cool,stressisplacedatthepointofattachment.Cyclicalstressesare
commoninrotatingmachinery,andcomponentsmayfailbyfatigue
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insuchlocations.Iffatiguestressesoccurinanenvironment
containingaggressivechemicals,fatiguefailuresareoften
accelerated.Thechemicalcanpenetratemetalatfatiguecracksto
increasethecrackingrate.
Intergranular
Corrosion:Intergranularcorrosion
occursalongthegrainboundariesof
metals.Thisattackisoftensetupby
poorheattreatmentofthemetal.
Improperheatingorcoolingofan
alloymayoccurduringthe
fabricationprocess,ormoreoften,
Intergranularcorrosionattackin
whenthematerialisbeingweldedin
austeniticcoldrolledstainlesssteel
thefield.Theextremeheat
sheet.Imagesource:Creative
generatedduringweldingcanalter
Commons
thecrystallinestructureofthealloy
andreducecorrosionresistance.Manystainlesssteelfailureshave
occurredduetopoorwelding,wheretheheatfromtheprocess
causeschromiumtocombinewithcarbonintosmallglobules.
Chromiumcarbideprecipitationreduceschromiumsabilitytoforma
protectiveoxidelayeronthesteelsurfaceandopensthewayfor
corrosion.
Dealloying:Dealloyingistheselectiveleachingofonemetalfroman
alloy.Twoofthemostcommonformsaredezincificationand
denickelificationofAdmiraltymetalandcoppernickelalloys,
respectively.Althoughdebateexistsastotheexactcorrosion
mechanism,theresultsaresimilar:Thezincornickeldeparts,
leavingaspongycoppermassbehind.
Exfoliation:Exfoliationisareadilyobservablephenomenonas
flakesofmetalappearonthepipeortubesurface.Theseflakeswill
oftenwashdownstreamandfoulotherareasofthesteamgenerating
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system.Exfoliationmaybetheresultofmechanicalfactorsmore
thanchemicalattack.Exfoliationiscommonlyobservedinhigh
temperaturetubesandpiping,wherethehightemperaturesgenerate
thickoxidelayers.Cyclicoperationplacesmechanicalstressonthe
deposits,andeventuallytheybegintobreaklooseandtransport
elsewhere.
MicrobiologicallyInfluencedCorrosion:Microbiologically
influencedcorrosion,orMICforshort,isacommonproblemin
coolingwatersystems.Microbesnotonlyformdepositsthatmay
causeunderdepositcorrosion,butmanyorganismsalsogenerate
corrosivechemicalsviametabolicprocesses.Typically,ifmicrobes
areallowedtoattachtoametalsurfaceandformacolony,the
organismssecreteprotectiveslimesforprotection.Whileorganisms
nearthesurfacemaybeaerobicbecauseoxygenispresentinthe
coolingwater,thecoloniesunderneathconsistofanaerobicbacteria.
Theseorganismslivebyusingmineralsinthewater,andthe
byproductoftheirmetabolicbiochemistrymayincludesulfuricacid,
hydrogensulfide,andothernasties.Localizedattackandpittingare
theresult.
Part2willdiscusssomeoftheprimarymetalsandtheirreactionto
corrosivemechanisms.InPart3wewillexaminecorrosionissues,
andincludeadiscussionofmethodsofcontrol.
Tocontacttheauthorofthisarticle,
emailengineering360editors@ieeeglobalspec.com

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