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Effectofintermetallicphasesoncorrosionresistanceof
superduplexandsuperausteniticstainlesssteelweldments
AJLeonard+,PWoollin+andDCBuxton*
+TWILtd
GrantaPark,GreatAbington,Cambridge,CB16AL,UK
*NowatCapcisLtd
CapcisHouse,1EchoStreet,Manchester,M17DP,UK

StainlessSteelWorldConferenceTheHague,Netherlands,1315November2001
Manuscriptnumber:P0185

Abstract
Superduplex,superausteniticandnickelalloyshaveexceptionalcorrosionresistanceandhaveprovenperformancein
manyaggressiveenvironments.However,thesehighlyalloyedmaterialsaresusceptibletotheformationof
intermetallicphaseswhenexposedtothermalcyclesintherange6001000Casmaytypicallybeexperienced
duringwelding.
Thestudyexaminedfouralloys:UNSS31254,S32760,S32750andN08825,whichwerewelded,usingan
overmatchingNiCrMofillerinthecaseofthesuperausteniticsteel,nickeloveralloyedsuperduplexfillersforthe
superduplexstainlesssteelsandAWSE/ERNiCrMo3typeconsumablesforalloyN08825.Weldswereproducedwith
differentlevelsofarcenergyrepresentingconditions:(i)wellwithintypicalindustrialpractice,(ii)atthetopendof
typicalindustrialpracticeand(iii)abovetypicalpractice.Thevolumefractionofintermetallicphasewasdetermined
foreachmaterialandweldingcondition.Thecorrosionperformanceoftheweldswasassessedusingshortterm
criticalpittingtemperaturetests,andalsousinglongtermtestsinsimulatedserviceenvironments:chlorinated
seawater,CO2/O2brine,CO2/H2Sbrineandasevererefineryenvironment.
Theresultsshowedthatusinggoodindustrialpractice,weldscontaininglessthan1%intermetallicwereproducedin
superduplexstainlesssteelandbetween1.4and2.4%weldmetalintermetallicwasformedinthehighlyalloyed
nickelbaseweldmetals.Inthecaseofsuperduplexconsumables,thisincreasedtobetween1.7and2.9%when
usingconditionsabovetypicalindustrialpractice.Theincreaseinarcenergywasassociatedwithareductionincritical
pittingtemperature.However,insimulatedserviceenvironments,theweldsshowednosignificantcorrosion.
Recommendationsaremadewithregardtothesettingoffitnessforservicecriteria.

1.Introduction
TheexcellentlocalisedcorrosionresistanceofsuperduplexandsuperausteniticstainlesssteelsandNiFeCralloys
stemsfromthehighlevelsofalloyingelements,inparticularCr,MoandN.However,thesehighlyalloyedmaterials
aresusceptibletotheformationofintermetallicphases,whichformattemperaturesbetweenaround600Cand
1000C.Suchtemperaturesareexperiencedduringaweldthermalcycle,givingthepossibilityofintermetallicsbeing
formedinweldments,especiallyforhighalloygrades,whereprecipitationcanbeginwithinafewtensorhundredsof
seconds[1,2] .
HighlyalloyedstainlesssteelsandNiFeCralloysaresusceptibletolocalisedcorrosion,e.g.pitting,inaggressive
chloridecontainingmediaandintermetallicprecipitationmayreducethecorrosionresistancesignificantly.
Intermetallicphasesarerichinalloyingelements,notablyCrandMo,comparedtothesurroundingmatrixand
therefore,astheintermetallicphaseisformed,CrandModepletedzonecanbecreatedaroundtheparticles.The
extentofthealloydepletionwilldependuponthethermalcyclesexperiencedandwilldeterminethereductionin
corrosionresistance[1,2] .Theaimsofthecurrentworkweretoquantifythevariationofintermetallicphase
formationoverarangeofweldingconditionsforsuperduplex,nickelandsuperausteniticalloys,andtodetermine
theireffectsoncorrosionresistanceinrealisticserviceenvironments.

2.Experimentalprocedure
2.1.Materials
Fourcorrosionresistantalloyswereselectedfortesting,i.e.onesuperausteniticgrade:UNSS31254,two
superduplexgrades:S32760andS32750,andoneNiFeCralloy:N08825.ThesearereferredtoasmaterialsAtoD
respectively.Thematerialswereinplateform,withanominalthicknessof10mm.Table1ashowstheirchemical
compositions.

2.2.Welding
TheTIGprocesswasutilisedfortherootandsecondpasses,whilstfillandcappingpassesweredepositedusingthe
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MMAprocess.Nopreheatingwasusedandinterpasstemperatureswererestrictedtobelow150Cinallcases.The
shieldingandbackinggaseswerebothargon.Typicalweldmetalcompositionsfortheconsumablesusedarelisted
inTable1b.AnovermatchingNiCrMofillerwasusedinthecaseofS31254,nickeloveralloyedsuperduplex
consumableswereusedforthetwosuperduplexgrades,andAWSE/ERNiCrMo3typeconsumableswereusedfor
alloyN08825.
Weldingcurrentandtravelspeedwerevariedtoproduceweldswiththreedifferentlevelsofarcenergy,i.e.low(L):
from0.9to1.6kJ/mm,medium(M):between1.1and2.0kJ/mmandhigh(H):between1.9and3.2kJ/mm,
representingconditions(i)wellwithintypicalindustrialpractice,(ii)atthetopendoftypicalindustrialpracticeand
(iii)abovetypicalindustrialpractice.
Theweldswerecodedwitha'W',followedby'A,B,CorD'torepresentthebasesteelandthen'L,MorH'.Where
morethanoneweldofeachtypewasmade,theseweredistinguishedbyanumber,e.g.1or2.

2.3.Characterisation
Twodifferentpointcountingmethodologieswereadoptedfordeterminingthelocalisedpeakandaveragevolume
fractionofintermetallicphasesineachweld:(i)Todetermine'peak'localisedprecipitatelevels:16measurement
fieldswerecountedonapreparedmetallographicspecimen,inasquare4x4fieldarray,inareasidentifiedbyprior
microscopicexaminationascontainingthehighestlevels,atamagnificationofeitherX1250orX1400.(ii)To
determineaverageprecipitatelevels:16measurementfieldswerecounted,usinga100point(10x10)grid,at
randomlocationswithintherootandsecondweldruns.ThemagnificationusedwaseitherX1250orX1400.The
phasebalancewasalsodeterminedineachofthefollowingareasofthesuperduplexmaterials:parentsteel,weld
metalcap,weldmetalroot,capHAZandrootHAZ.

2.4.Shorttermferricchloridecorrosiontests
Criticalpittingtemperature(CPT)ferricchloridetestswereconductedgenerallyfollowingASTMG48MethodC[3] .
Theweldsurfaceswereleftasweldedexceptfordegreasing,andthespecimenssidesandendswerepreparedto120
and1200gritfinishrespectively.Exposurecommencedat27.5C.Thetemperatureincrementwas2.5C.This
procedurewasrepeateduntileithermetallosswasdetectedbyvisualinspectionorweightlossexceeding20mgwas
recorded.ThefirsttemperatureatwhichpittingoccurredwastakenastheCPT.

2.5.Longtermcorrosiontestsinsimulatedserviceenvironments
2.5.1.Testsamples
Thespecimenswere~25by50mmbyfullthickness,sothattheexposedsurfacesincludedbothweldcapandroot,
andcutedges.Theweldsurfacesweredegreased,whilstthespecimenedgesandendswerepreparedto120and
1200gritfinishrespectively.Specimenmasswasrecordedbeforeandaftertest.Followingcompletionofthe
corrosiontest,sampleswereexaminedvisuallyandifsignsofcorrosionwereobserved,examinationinascanning
electronmicroscope(SEM)wasundertaken.

2.5.2.Chlorinatedseawatertest
Duplicateweldsamplesofthesuperausteniticandbothsuperduplexgradeswereimmersedinnaturalseawaterheld
ataconstanttemperatureof40C.Thetestvesselwasopentotheatmosphere,allowingdiffusionofoxygeninto
thetestsolution.Adilutedsolutionofsodiumhypochlorite(approximately1%)wascontinuouslyaddedtothetest
solution,toachieveafreechlorinelevelbetween0.5and1.0ppmthroughoutthetest.Electrochemicalpotentialwas
recordedduringtheexposureperiod.
After36and62daysexposure,thespecimenswereremovedandinspectedvisuallyunderabinocularmicroscope.
Masslossmeasurementsweretaken.Asnoevidenceofcorrosionwasfound,thetesttemperaturewasincreased
from40Cto53Conreimmersionafterthesecondinspectionuntiltheendofthetestonday91.Following
removalfromthetestsolution,thespecimenswerecleanedinwater,inspectedunderabinocularlightandre
weighed.

2.5.3.CO2/O2Brinetest
TheCO2/O2containingbrinewasdesignedtosimulateproducedwatersystemswheretemperaturescanbehigh(80
100C)andsmallamountsofO2canbepresent.Specimensofsuperausteniticsteel(UNSS31254),oneofthe
superduplexgrades(UNSS32750)andtheNiFeCralloyN08825weresuspendedindeaerated3%NaClsolutionat
80C,agasmixtureofCO2and0.4%O2wasintroducedandbubbledthroughthesolutionthroughoutthe90day
testperiod.Thetotaltestpressurewas2.5barg,whichgaveapartialpressureofCO2of2bar.Followingcompletion
ofthetest,thespecimenswerecleanedinwater,inspectedvisuallyandreweighed.Themasslossforeachspecimen
wasalsodeterminedafterasecondcleaningoperation,using40%hydrochloricacidtoremovetarnishing[4] .

2.5.4.CO2/H2Sbrinetest
TheH2ScontainingenvironmentwaschosentomatchtheNACEMR017599recommendedservicelimitsforUNS
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S32760[5] .Thetestsolutioncompriseddeaerated12%NaCl,withanadditionof0.34g/lofsodiumbicarbonateto
giveapHvalueof4,attesttemperatureandpressure.Fourpointbendtestspecimensweretakenfromthetwo
superduplexgrades.Thespecimenshadtherootintactandwerestrainedtogive0.2%plasticstrainattheweldtoe.
Afterheatingtotesttemperature,i.e.100C,theCO2/H2S/N2testgasmixwasintroducedtothevessel,providing
CO2andH2Spartialpressuresof2and0.2bar,respectivelyandthetestlasted90days.Attheendofthetest
period,thespecimenswereinspectedasdescribedinsection2.5.2above.

2.5.5.Severerefinerytest
ThetestinvolvedpreparationofNH4Clpaste(160mlofdistilledwaterand330gofNH4Cl),whichwasplacedina
glasscontainerinsideanautoclave.Approximatelyonelitreofdistilledwaterwaspouredintotheautoclave.After
sealing,thesystemwaspurgedwithN2gastoremoveoxygenpriortotesting.Twosetsofspecimenswere
employed:onesetwasplacedinthepaste,theotherwassuspendedinthevapour.Allfourmaterialswereincluded
inthetest.Theautoclavewasheatedtoatemperatureof148Candwaspressurisedto18bargwithN2gas.The
testdurationwasonemonth.Thewaterinthebottomofthevesselprovidedapproximately20%humidityinthe
vapourphase,assumingawatervapourpartialpressureof4.5bar.Followingunloadingoftheautoclave,the
specimenswerewashedinwater,visuallyinspectedforevidenceofcorrosionunderabinocularmicroscopeandre
weighed.

3.Results
3.1.Metallography
3.1.1.MaterialA:superaustenticsteelUNSS31254
EachoftheweldmetalsofmaterialAcontainedwidespreadinterdentriticintermetallicphases,thevolumefractionof
whichgenerallyincreasedwithincreasingarcenergy,Tables2and3.Thepeakvolumefractionincreasedfrom1.8%
to2.4%.Mostdenseprecipitationwasinreheatedareas.Theweldcapandbandsinthelowerpartsofreheated
passesshowedlessprecipitation.Theaveragevolumefractionofintermetallicswaslower,butshowedasimilartrend
tothepeakvolumefractionresultsincreasingfromlowarcenergy(1.4%)tohigharcenergy(1.8%).Figure1shows
atypicalmicrostructureoftheweldrootinthehigharcenergyweld.Theintermetallicparticleswereirregularin
shapeandtypically1mto4minalldimensions.NoHAZprecipitationcouldbequantified,although,therewas
evidenceofpreferentialetchingoftheHAZgrainboundariesandathigherarcenergiessome'spottiness'and
thickeningoftheboundarieswhenetched.

Fig.1.Typicallightmicrographoftherootmicrostructureof
UNSS31254weldWAH1

3.1.2.MaterialB:superduplexsteelUNSS32760
AllweldsinmaterialBshowedatypicalferriteaustenitestructure,withislandsofausteniteinaferritematrix.Some
smallpatchesofsecondaryaustenitewerepresent,typicallylyingbetweenweldpasses,andmostnumerousforthe
deliberately'abusive'weldprocedures,i.e.themediumandhigharcenergy.Theferritevolumefractionsforeachof
theweldsareshowninTable4.Thereportedvalueswerewithintheexpectedrange[6] .
Weldsofmediumandhigharcenergybothcontainedintermetallicphasesinaregionencompassingtherootand2nd
weldpasses.Inthesesamples,thepeakvolumefractionswere0.8%and1.7%respectivelyinthemiddleofthe
areasofprecipitation(Table2).Randompointcountinggaveaveragevolumefractionsintherootandsecondpass
of0.6%and0.5%respectively(Table3).Thelowarcenergyweldcontainedonlyafewparticlesintheweldroot,
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possiblyintermetallics.Figure2showstherootbeadmicrostructureinsampleWBH1.Theintermetallicparticleswere
irregularinsizeandmorphology,Fig.2b,andtendedtobeelongatedontheausteniteferriteinterfaces.Typical
exampleswere12mwideanduptoaround10minlength.

a)lightphotomicrograph

b)backscatteredelectronimageofintermetallicphase

Fig.2.MicrostructureoftherootofWBH1UNSS32760welds

TheHAZcontainedprecipitates,withmorphologysuggestingthatsomewerenitridesandsomeintermetallics.Allof
thedifferentarcenergysamplesshowedsimilarhightemperatureHAZfeatureswithgroupsofetchpitswithin
ferriticgrainsanddecorationofferritesubgrainboundaries.Theseareconsistentwithchromiumnitrides.

3.1.3.MaterialC:UNSS32750
Eachweldcontainedasmallfractionofintermetallicphases,predominantlyinthesecondweldrunandsomesmall
regionsofsecondaryaustenitetowardstheweldcap.ThehightemperatureHAZshowedlimitedfineintragranular
nitrides,butnointermetallicphaseswerefound.TheferritevolumefractionineachweldisshowninTable4andwas
withintheexpectedrange[6] .
Thepeaklevelofintermetallicphaseswashighestin.themediumarcenergyweld.Thiswasdeterminedtobe2.6%
c.f.0.8%inthelowarcenergysampleand1.3%inhigharcenergysample(Table2).However,randompoint
countingrevealedloweraveragevolumefractions,whichincreasedwithincreasingweldarcenergy,Table3.Asfor
S32760,typicalprecipitateswere12mwideanduptoaround10minlength.

3.1.4.MaterialD:NiFeCralloyUNSN08825
Alloftheweldmetalscontainedsecondphaseinterdendriticparticles,whichwasfairlyuniformthroughouttheweld
metal.ThevolumefractionsoftheintermetallicphaseparticlesaredisplayedinTables2and3,andincreaseslightly
withincreasingarcenergy.
ExaminationintheSEMconfirmedthepresenceofsecondphaseparticlesofirregularmorphologyandwith
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dimensionsupto5m.TheHAZprecipitationcouldnotbequantifiedintermsofsizeorvolumefraction,butthe
grainboundariesinthiszoneshowedpreferentialetchingwhencomparedtoparentmaterial,becomingincreasingly
pronouncedathigherarcenergy.

3.2.Ferricchloridetesting
TheresultsaredisplayedinFig.3.ThesuperausteniticsteelsamplesgavethehighestCPTvalues,upto55C,whilst
pittingwasfirstobservedonthesuperduplexalloysattemperaturesbetween35and40C.Generally,astheweld
arcenergyincreased,theCPTwasreduced,althoughtherewaslittledifferencebetweenthemediumandhigharc
energysamples.Theparentmaterialcriticalpittingtemperaturescalculatedfrompublisheddata[3] werefoundtobe
approximately60C.Inallcases,themeasuredweldvalueswerebelowtheparentmaterialvalue,aswouldbe
expected.

Fig.3.FerricchlorideCPTdata

ThelocationofattackwasfoundtovarywiththeUNSS31254specimensmainlysufferingcorrosiononthespecimen
sidesatthefusionline.Forthetwosuperduplexgrades,attackwasagainonthespecimensides,generallyinthe
rootorsecond/thirdpassweldmetalregion.

3.3.Longtermcorrosiontestsinsimulatedserviceenvironments
3.3.1.Chlorinatedseawatertest
Theweightchangeresults,displayedinFig.4,weresmall,whichindicatesthatnosignificantcorrosionoccurred
duringthetestperiod.Inaddition,therewasnosignificantdifferencebetweenthelowandhigharcenergyweld
results.Themasslossincreasedwithtimeandthemaximumrecordedmasslossforthe91dayexposurewas
5.7mg.Thisrepresentsaverylowuniformcorrosionrateof<0.001mm/yr.Thevisualexaminationresultssupport
theweightchangedata,astheinspectionafter36daysexposureonlyrevealedsomeweldmentdiscolourationand
lightetching,whichrevealedtheweldmetal.

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Fig.4.Masslossresultsfromthechlorinatedseawatertests

ThecorrosionpotentialsthatwererecordedduringthetestperiodareplottedinFig.5a,bandc.Theinitialpotential
readingswereapproximately200to300mVSCE,butduringthefirstfewdaysofthetest,thecorrosionpotentials
ofthespecimensincreasedtovaluesabove0mV.Duringthethreemonthtest,potentialsof+500to+600mVwere
recordedonallthealloys.However,thepotentialswerenotsteadyandsignificantfluctuationswereobserved.Typical
behaviourisshownintheplotoftimeversuscorrosionpotential,Fig.5d,whichwasrecordedafter19daysexposure.

a)UNSS31254

b)UNSS32760
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c)UNSS32750

Fig.5.Corrosionpotentialsduringthechlorinatedseawatertests:

PotentialfluctuationinUNSS31254

3.3.2.CO2/O2brinetest
Afterexposure,allofthetestspecimensappearedtarnishedbrown,withsomeblackdiscolorationaroundtheweld
cap.Therewasnovisualevidenceofpittingcorrosionorofanycrevicecorrosionwherethespecimenshadbeen
supported,butsomecorrosionatweldspatteronthecaphadoccurred.
ThemasslossresultsaregiveninTable5andaregenerallylow,indicatingnocorrosionattackwiththeexceptionof
WCL1andWCH2F2.Theresultsafterlightbrushingshowedasmallweightgain,probablyreflectingthebuildupof
theFe/Croxideontheweldmentsurface.Furtheroxidationoftheweldoxidesduringthecorrosiontestcouldleadto
anincreaseinweightandabrowndiscoloration.ThemasslossesrecordedaftercleaninginHClsuggestedthatthese
oxideswereremoved.ThelossesrecordedforspecimensWCL1andWCH2F2werenotaccompaniedbyanyvisual
evidenceofcorrosionandareconsideredunlikelytobetheresultofcorrosionattack,butmorelikelytobecausedby
theremovalofweldoxidesandweldspatter.Asimilarmagnitudemasslosswasobservedinaferricchloridetest,
duringinitialexposure.

3.3.3.CO2/H2Sbrinetest
MasslossdataaregiveninTable6.Thevisualexaminationperformedafterthetestdidnotrevealanyevidenceof
corrosionattackandallthespecimensweresimilarinappearance.Allthespecimenssufferedsomemasslossduring
thetestperiod(Table6).Themaximumvaluewas34mgonspecimenWBH1F4,butasfortheCO2/O2brinetest,as
therewasnovisualevidenceofcorrosion,themasslossisbelievedtoarisefromlossofweldoxide.Althoughthe
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differencesweresmall,higharcenergyweldsgavehigherweightlossthanthelowarcenergywelds.TheS32760
steelweldsshowedgreaterweightlossthantheS32750steel.

3.3.4.Severerefinerywatertest
Themasslossresults,whicharedisplayedinTable7,areverylow.Visualexaminationconfirmedthatminimal
corrosionhadoccurred.

4.Discussion
4.1.Precipitationcharacteristics
Overthearcenergyrangeexamined,thevolumefractionofintermetallicphaseinnickelbasedweldmetalsincreased
byonlyupto50%,whilstsuperduplexweldmetalsshowedanincreasefromlessthan0.5%toaround2.6%
maximum.Itshouldbenotedthatthehighestarcenergiesemployedwerewellbeyondthemanufacturers'
recommendedlevelsandequallybeyondthemaximumlevelsthatwouldtypicallybeexpectedforindustrialwelding.
Perhapsofgreatersignificanceisthefactthatindividualparticlesizesvariedlittlebetweenthedifferentarcenergy
levels.Forsuperduplexweldmetal,particlestendedtogrowalongaustenite/ferriteboundariesandbecomemore
numerousbutthewidthofparticlesvariedlittlewitharcenergy.Nickelbasedweldmetalsgenerallyshowed
increasednumbersofparticlesratherthanlargerparticlesathigherarcenergy.Singlephasewelddepositstransform
tointermetallicphaseinalloyenrichedinterdendriticareasanddendritesizewasrelativelyconstantforthewelds
examined,typicallyrequiringorderofmagnitudechangesincoolingrateforsignificantchangestooccur.In
superduplexdeposits,intermetallictendstoforminthinareasofferritebetweentwoislandsofaustenite.As
austeniteessentiallydoesnottransformtointermetallicphase,theparticlesizeislimitedtosomeextentbythe
spacingofausteniteunits.

4.2.Corrosionresistance
4.2.1.Ferricchloridetests
AgeneralreductionintheCPTvalueswasobservedforthethreealloysA,BandCasthearcenergyincreased.
However,thereductionwasnotlargesignificantdropsinCPTcomparedtoparentplatematerialbehaviour,upto
40C,havebeenreported[7] forvolumefractionsof1to4%intermetallicphaseproducedinsuperduplexsteelby
isothermalheattreatment(Fig.6).However,thescatterinthispublishedplotofdropinCPTversusvolumefraction
ofintermetallicisconsiderableandthisisconsistentwiththesizeofindividualprecipitatesbeingmoreinfluentialthan
thevolumefraction[1,2] .Thetemperatureatwhichtheprecipitateisformedwillalsohaveaneffect.Forpitting
resistancetobereduced,thedepletedlayermustbeofsufficientsizetocontainastablepitnucleusandthewidthof
thedepletedlayerandtheextentofalloydepletionareafunctionofdiffusionrates.Hence,depletedlayerwidthhas
beensuggestedtobethefactorcontrollingcorrosionresistance,ratherthanvolumefraction.Forexample,thesizeof
astablepitnucleusmightbe0.1m[8] .Ithasbeenshownthatprecipitatesproducedbyisothermalageing,which
arelargerthanthoseformedduringwelding,aremoredetrimentaltoCPT,foragivenvolumefraction[1] .

Fig.6.EffectofintermetalliccontentonCPTreduction[3]

ThepresentdataisincludedwiththepublisheddatainFig.6anditfallswithinthescatterband.Thedatahasbeen
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plottedtwicefirstlybyusingpublishedparentmaterialCPTvaluestocalculatethereductioninCPT(theparent
materialvaluewas~60CforallthesealloysS31254,S32760andS32750)andthe'peak'intermetallicvolume
fractionresults,andsecondly,bytakingthedifferencebetweenthelowandhigharcenergyweldferricchloride
resultsandusing'average'intermetallicvolumefractiondata.Itmustberecognisedthatwhencomparingtheweld
andparentmaterialCPTvalues,thesignificantreductionisnotentirelytheresultofintermetallicformation.Thetwo
methodsofdepictingthedatainFig.6representthetwoextremesthatmightbeconsidered.
Whilstintermetallicprecipitationwasmorepronouncedinthenickelwelddeposits,theyweresufficientlyoveralloyed
thatsubstantiallossofcorrosionresistancewouldberequiredtobringtheweldmetaldowntotheparentsteellevel.
Hence,inthesuperausteniticandNiFeCralloyweldments,thecorrosionresistancewasmuchmorelikelytobe
controlledbytheHAZorfusionline,whereprecipitationorformationofanunmixedzone(UMZ),withassociatedMo
segregation,mayoccur.TheformationofaUMZ,whichconsistsofmeltedparentmaterialwhichhasnotmixedwith
theconsumable,anditspotentiallylimitingeffectoncorrosionresistanceforweldsinUNSS31254hasbeenwell
documented[9] .Inthesuperausteniticalloytheattackwasobservedonthespecimensideatthefusionlineandis
believedtobeassociatedwiththepresenceofaUMZwhichhaspreviouslybeenfoundtobetheareaoflowestpitting
resistanceforweldsinthismaterial[9,10] .Furthermore,thereductionincorrosionresistancethatisassociatedwith
thepresenceofweldingoxideandthechromiumdepletedlayerontherootandcapsurfaceappearstobeless
significantthantheeffectoftheUMZinthisinstance.
Forthetwosuperduplexgrades,attackwasalsoonthespecimensides,generallyintherootweldmetalregionor
aroundmidthickness,equivalenttothesecond/thirdpasses.Theseareaswereassociatedwiththehighest
concentrationofintermetallicphases.Theresultsindicatethattherootsurface,whichisnormallythesurfacethatis
exposedtotheenvironment,hasabetterpittingresistanceinaG48testthantheweldmetalonthespecimensides.
Thisprobablyreflectsthefactthatintermetallicphasesdonottendtoformontherootsurfacebutconcentrate
furtherintotheweld,althoughinthehigharcenergyS32760,weldintermetallicphasewasobservedadjacentto
theweldroottoes.However,attackwasnotobservedatthatlocation.
Theferricchloridetestisaverysevereacceleratedcorrosiontestandalthoughitisusedtorankcorrosion
performanceofalloys,thesignificanceofanycomparisonwithcorrosionresistanceinquitedifferentservice
conditions,e.g.asemployedinthelongtermcorrosiontests,isopentoquestion.

4.2.2.Effectofintermetallicphaseoncorrosionresistanceinserviceenvironments
Noseverecorrosionwasobservedinthelongtermtestsconductedinsimulatedserviceenvironments.Thetest
environmentsrepresentedservicelikeconditionsandwereconsideredareasonablyseveretestoftheweldment
performance.
Thechlorinatedseawatertestcommencedat40C,10CabovetheNORSOKstandardlimit[11] andbecauseno
corrosionwasdetectedthetemperaturewasincreasedto53C.ItisrecognisedthattheNORSOKlimitisconsidered
severeandthatthetestspecimensmayhavebeen'conditioned'tosomedegreebyexposuretothelowertest
temperature,butoverallitisconsideredthatthetesthasdemonstratedthecorrosionresistanceofthewelded
specimenstochlorinatedseawater.
PrevioustestsinCO2/O2containingbrinehavebeenreportedbyRogneandJohnsen[12] .Theyconsideredthatat
80Cand200ppbO2,localisedcorrosiononS31254mightinitiateandamaximumservicetemperatureof60Cwas
recommendedforweldedS31254,if200ppbO2ispresent.Thetestconditionsusedwerethereforemoreseverethan
thoserecommended,yetnocorrosionwasobserved.
TheCO2/H2SbrineandNH4CltestswerebasedonconditionsfromNACE[5] andindustrialexperiencerespectively
andwereconsideredfairlydemanding.Thebendsamplessubjectedtothesourtestdidnotshowanyevidenceof
corrosionorcrackingandtheunstrainedsamplesshowednosignificantcorrosion.Similarbehaviourwasobservedfor
theNH4Cltests.Modestmasslosses,upto65mg,wereobservedonanumberofspecimens.However,therewasno
visualevidenceoflocalisedcorrosiononanyofthesespecimensanditisbelievedthatthemasslossaroselargely
fromremovalofweldspattereitherduringthetestorposttestcleaning.
Insummary,boththelowandhigharcenergyweldsampleshadsufficientcorrosionresistancetowithstandthe
chlorinatedseawater,CO2/O2brine,CO2/H2SandNH4Cltestenvironments.Therefore,materialswithintermetallic
phaseofsimilartypeandatcomparablevolumefractionswouldbeconsideredsuitableforserviceinthese
environments.Corrosionattackofthehigharcenergyspecimensmighthavebeenexpectediftheweldingprocess
hadproducedintermetallicphasethatsignificantlyreducedcorrosionresistance.However,theshorttermtests
indicatedthattheeffectoftheintermetallicwasfairlysmall.
Theintermetallicphasevolumefractionsproducedinthisworkwerelowwhencomparedtolevelsgeneratedby
isothermalageing,buttherangeofarcenergywasbroadandwentwellbeyondcurrentrecommendedwelding
practice.

4.3.Practicalimplications
Foroptimumsuperduplexweldmentcorrosionresistance,weldingconditionsshouldberestricted,e.g.to0.5to
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1.5kJ/mmarcenergyand<100Cinterpasstemperature,tominimiseintermetallicphaseformation.Superaustenitic
alloyUNSS31254andNiFeCralloyN08825,donotrequiresuchclosecontrolofweldingconditionstominimise
weldmetalintermetallicformation,butlowerarcenergygivesimprovedcorrosionresistance,perhapsbyminimising
HAZprecipitationandUMZsegregation.
Metallographicexaminationforintermetallicphaseistypicallyapartofweldprocedurequalificationforsuperduplex
stainlesssteels.Whensomeparticlesareformed,pointcountingisoftenperformed,andattemptsmadetosetan
allowableupperlimit,typicallyaround12%.However,thesizeoftheprecipitatesisperhapsofsignificanceaslarger
particlesareexpectedtoproducegreaterdepletedzones.Fromthiswork,weldswith23%intermetallicphasemay
beconsideredforcorrosionresistantservice.Demonstrationoffitnessforpurposeshouldbeonthebasisofrealistic
simulatedworstcaseservicetests,ratherthanshorttermqualitycontroltypetests.

5.Conclusions
1. Generallytheintermetallicvolumefractionincreasedwithincreasingarcenergyinsuperduplex,
superausteniticstainlesssteelsandnickelalloys.
2. Weldsinsuperduplexsteel(UNSS32760andS32750)hadweldmetalintermetallicvolumefractionsless
than1%whenweldedwithintypicalgoodindustrialpracticelimits.
3. Weldsproducedwithhigharcenergy,upto3.2kJ/mm,i.e.abovetypicalindustrialpractice,hadmaximum
weldmetalintermetallicvolumefractions,between1.7%and2.9%.
4. Interdendriticintermetallicprecipitatesformedinhighlyalloyednickelbaseweldmetals.Whentypicalgood
industrialpracticewasfollowed,thevolumefractionofintermetallicwasbetween1.4and2.4%.
5. Littlevariationofintermetallicparticlesizewitharcenergywasobserved.
6. Thecorrosionresistanceofweldspecimenscontainingintermetallicprecipitatesproducedbyweldingwitharc
energywellabovetypicalindustriallimits,wasreducedbyamodestmargininshorttermpittingtests,butin
simulatedserviceenvironments,nodifferenceincorrosionperformancewasrecorded,asnoneofthesamples
showedsignificantcorrosion.

6.Acknowledgements
ThisworkwasfundedbyAvestaPolarit,BPExplorationOperatingCoLtd,DERA,ESABAB,EssoEngineering(Europe)
Ltd,FabriquedeFerdeCharleroiSAandShellUKExplorationandProduction.Thesupportofthesponsorsis
gratefullyacknowledged.TheauthorsalsowishtothankalltheircolleaguesatTWIwhoassistedwiththepractical
work.

7.References
1. FrancisR:'DiscussiononinfluenceofphaseongeneralandpittingcorrosionresistanceofSAF2205duplex
stainlesssteel'.BritCorrJ199227(4)319320.
2. GoochTG:'Corrosionbehaviourofweldedstainlesssteel'.WeldJ199675(5)135154.
3. ASTMG48971:'Standardtestmethodsforpittingandcrevicecorrosionresistanceofstainlesssteelsand
relatedalloysbyuseofferricchloridesolutions'.
4. NACEPublication3M182:'CorrosionTestingofChemicalCleaningSolvents'.
5. NACEMR017599:'Standardmaterialrequirementsforsulphidestresscrackingresistantmetallicmaterials
foroilfieldequipment'.
6. GunnRN:'Duplexstainlesssteels'.AbingtonPublishing,Cambridge,1997,118.
7. GunnRN:'Effectofthermalcyclesonthepropertiesof25%Crduplexstainlesssteelplatespreliminary
studies'.TWIMembersReport505,1995.
8. MattinSP:'Nucleationofcorrosionpitsinstainlesssteel'.PhDdissertation,CambridgeUniversity,1994.
9. GoochTGandElbroAC:'Weldingcorrosionresistanthighalloyausteniticstainlesssteel'.ProcCorrosionin
NaturalandIndustrialEnvironments:ProblemsandSolutions,Grado,Italy,NACEInternationalItalia,Monza,
1995,351.
10. StenvallP,LiljasMandWallenB:'Performanceofhighmolybdenumsuperausteniticstainlesssteelweldsin
harshenvironments',ProcCorrosion'96,DenverUSA,NACEHouston,1996,paper419.
data:text/htmlcharset=utf8,%3Cdiv%20class%3D%22ContentEditor%22%20style%3D%22color%3A%20rgb(0%2C%200%2C%200)%3B%20fontfam

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11. NORSOKStandardM001Rev.2November1997:'MaterialsSelection'.
12. RogneTandJohnsenR:'TheeffectofCO2andO2onthecorrosionpropertiesofUNSS31254andUNS
S31803inbrinesolution'.ProcCorrosion'92,NACEInternational,Houston,paper295.

Table1aChemicalanalysesofeachoftheparentmaterials.

Material
S31254
(A)
S32760
(B)
S32750
(C)
N08825
(D)**

Si

Mn

Element,%(m/m)
P
S
Cr Cu Mo

Ni

PREN/PREW

0.014 0.40 0.40 0.020 <0.001 20.1 0.67 6.23 18.0 0.05 0.210

44.0

0.03 0.38 0.64 0.027 0.003

25.4 0.62 3.53 7.1 0.64 0.203+

41.4

0.02 0.21 0.78 0.025 0.002

24.8 0.29 3.84 6.8 0.06 0.264

41.7

0.010 0.30 0.69 0.018 <0.001 22.5 1.85 3.31 bal

0.05 0.010

33.6

**Ti0.62**Nb0.01**Fe30.5**Al0.09

Table1bWeldingconsumables

Parent
material
S31254
(A)
S32760
(B)

S32750
(C)

N08825
(D)

Typicalweldmetalchemical
composition
Consumabletype
Elements,wt%
C
Si
Mn Cr
Ni Mo Other
NiCrMowire
0.02 0.20 0.5 23.0 60.0 16.0
NiCrMoelectrode
0.02 0.3
0.7 25.0 Bal 15

Superduplexwire
0.015 0.4
0.7 25
9.3 3.7 W0.6

Cu0.7

N0.23
Superduplexelectrode 0.03 0.3
0.7 25
9.3 3.6 W0.7

Cu0.7

N0.23
SuperduplexTIGwire 0.02 0.3
0.4 25.0 9.5 4.0 N0.25
Superduplex
0.03 0.5
1.0 25.0 9.5 3.6 N0.22
electrodes

NiCrMoelectrodes
0.03 0.2
0.2 26.5 Bal 14

ERNiCrMo3
<0.03 <0.02 <0.5 22
65
9
Nb3.5
ENiCrMo3
<0.03 0.4
0.4 21.0 64
9.5 Nb3.3

Fe3.0

Table2Peakvolumefractionofintermetallicphase(%)countedsystematicallyina4x4fieldarray.

Peakvolumefraction(%)
Lowarcenergy Mediumarcenergy Higharcenergy
1.8
2.1
2.4
A(UNSS31254)
(0.70)
(0.7)
(0.8)
0.2
0.8
1.7
B(UNSS32760)
(0.4)
(0.7)
(1.0)
Parentmaterial

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C(UNSS32750) 0.8
(0.7)
2.3
D(UNSN08825)
(0.7)

2.6
(1.1)
2.8
(0.6)

1.3
(0.8)
2.7
(0.8)

Figuresinparenthesesare95%confidencelimits

Table3Volumefractionofintermetallicphase(%)countedrandomlyacross16fields.

Parentmaterial
A(UNSS31254)
B(UNSS32760)
C(UNSS32750)
D(UNSN08825)

Averagevolumefraction(%)
Lowarcenergy Mediumarcenergy Higharcenergy
1.4
1.9
1.8
(0.8)
(0.9)
(0.8)
0.3
0.6
0.5
(0.2)
(0.5)
(0.4)
0.2
0.3
0.4
(0.2)
(0.2)
(0.5)
2.4
2.4
2.9
(0.6)
(0.5)
(0.8)

Figuresinparenthesesare95%confidencelimits

Table4Ferritevolumefraction(%)ineachsuperduplexweld.

Parentsteel WeldmentID
B
WBL1
(UNSS32760)

WBM1

WBH1

C
WCL1
(UNSS32750)

WCM1

WCH1

Ferrite%
Parentmaterial Cap Root CapHAZ RootHAZ
49 46
62
55

(7) (5) (6)

(7)
51 40
60
60

(7) (4) (7)

(7)
53
48 42
67
58
(7)
(7) (3) (6)
(8)
44 41
56
44

(5) (3) (5)

(4)
47
43 45
55
49
(7)
(5) (4) (5)
(6)
44 44
51
45

(4) (5) (5)

(5)

Figuresinparenthesesare95%confidencelimits

Table5MasschangeresultsforCO2/O2brinecorrosiontest

Masschangeafterbrushing
Material
lightly
(mg)
A
WAL1F4 +10
(UNS
WAM1F2 +10
S31254)
WAH1F4 +13
C
WCL1
+0
(UNS
WCH2F2 +12
S32750)
D
WDL1
+12
(UNS
WDH1
+11
N08825)
Sample
ID

Masschangeaftercleaning
inHCl
(mg)
9
20
6
44
65
7
8

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Table6MasslossresultsfortheCO2/H2Sbrinecorrosiontest

Material

SampleID

WBL1F4
B
WBM1F2
(UNSS32760)
WBH1F4
WCL1F4
C
WCH1F3
(UNSS32750)
WCH2

Massloss
(mg)
21
13
34
4
8
5

Table7Masslossresultsforthesevererefinerywatercorrosiontest

Material

SampleID

WAL1P
A
WAL1V
(UNSS31254) WAH1P
WAH1V
WCL1P
C
WCL1V
(UNSS32750) WCH1P
WCH1V
WDL1P
D
WDL1V
(UNSN08825) WDH1P
WDH1V

Massloss
(mg)
6
5
8
3
9
9
8
3
4
3
1
2

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