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Ammonia scc

II. Ammoniacal SCC


Ammoniacalcompoundsaregenerallybelievedtobetheprincipalserviceenvironments
causingSCCincopperalloys,althoughtheseareknownnottobetheonlyones.SCCinthe
copper/ammoniacalsystemhasoftenbeentermed"seasoncracking"byleadingauthorities,
butthereisalackofunanimityindefiningthistermbyvariousauthorsandnomenclature
committees.Therefore,toavoidanypossibleconfusion,theterm"ammoniacalSCC"willbe
usedhereinstead,thoughevensoitshouldbeunderstoodthattheword"ammoniacal"isa
convenienceintendedtoincludeaminesandallotherspecieswhichcanreactwithcopperto
producethecupricammoniumcomplexionorperhapsstructurallysimilarcomplexes.
IfonelearnshowtoavoidammoniacalSCC,alargeproportionofthepracticalSCCthreatto
copperalloyscanbeprevented.NotonlyisammoniacalSCCamajorhazardtocopper
alloys,butitisalsotheSCCsystemforwhichwehavebyfarthemostintercomparable
laboratorydataandfieldexperience.WewillthereforetreatammoniacalSCCasthe
principaltopicofthischapter,thereaftertreatingtheotheralloy/environmentsystemswhich
donotfitintothemajorgroup.Theseothersystems,thoughtheyhavebeenresponsible
historicallyforfewerSCCfailuresthanammoniacalSCC.lessbeextremelytroublesome,as
willbeseen.Itshouldbeespeciallynotedthatrecentstudieswithcoppersulfateandcopper
nitratesolutionssuggestthatsomeoftheservicefailuressurmisedtohavebeencausedby
ammoniamayhavebeencausedratherbysulfateornitrateionsunderconditionspermitting
thegenerationofconcentratedcoppersolutions.AlsosomeoftheSCCfailuresoccurringin
theatmosphereandattributedtoammoniamayhavebeencausedinsteadbysulfurdioxide,
oxidesofnitrogen,orothercontaminants,asdiscussedunder"SCCinOtherEnvironments"
below.

Ammoniainsomeformisthefifth(andalsoobvious)conditionnecessarytocause
ammoniacalSCC.Therearealmostunbelievablydiverseandobligingsourcesofammonia,
includingthedecayofallsortsofbyproductsofmanylivingorganismsandthedecayofthe
organismsthemselves,electricalstorms,sparkdischarges,somesolderingfluxes(NH4C1),
andagriculturalandindustrialchemicals.ThreeexampleswhichhavecausedSCCinphos
phorizedcoppertubingusedinheatingsystemswillillustratethediversityofammonia
sources:(a)aminesusedasfoamingagentsinfoamedconcreteusedtoinsulateunderground
pipes,(b)latexadhesivesusedtolayvinyltileonfloorspiercedbycoppertubing,and(c)
ammoniacontainingagentsusedtocleanthosefloors.Notonlycanammoniabeproduced
byawidevarietyofreactions,butadditionallythereissomeevidencethattheammoniaso
producedindilutesolutioncanbeconcentratedincorrosionpitsbyanunexplainedprocess.
ItisnotuncommonforevidenceofammoniasurmisedtohavecausedSCCtobemissingat
thetimeforanalyzingafailure,whichmaybedonelongafterthecrackeditemhasbeen
removedfromtheenvironmentcausingcrackingandhasbeendried.Moreonthisbelow,
(ref.[4])
Notealsothatanarticlesuchasacondensertubemaybeadequatelyannealedorstress
relievedonlytohavestressesofdangerouslevelreintroducedbystraightening,denting,
cuttinganddeburring,orimproperinstallation.Forthesereasonsconservativepracticedoes
notrelysolelyonannealingtoavoidSCC.
Unfortunatelytoverifyadequateannealingforstressreliefthereisnopracticalalternativeto
potentiallydestructivetests,thoughonemayelecttooverannealandtherebysoftenthealloy

enoughthathardnessormicrostructurecanbeusedasevidenceofthestressrelief.
Conservativepracticelimitsstraighteningbrasstubingafterfinalannealingto2plane
straighteninganddisallowsrotarystraightening.
(4)Analloyofsusceptiblecompositionandstructureisafourth(andobvious)condition
whichmustbe
ThepresenceofCO2isnotanecessaryconditionforcracking,butitisobservedtospeedup
theprocessmarkedly.Corrosionpitsorotherstressintensifiersalsodonotseemtobe
necessaryconditionsforinitiatingammoniacalSCC,butsomeserviceexperiencesuggests
thatplugtypedezincificationmayspeeduptheinitiation.Corosionpitsmayalsoactas
ammoniaconcentratorsand/orconcentratorsofotherchemicalspecies.

AmmoniahascausedtwotypesofSCCinrefineriesandpetrochemicalplants.
Thefirstiscrackingofcarbonsteelinanhydrousammoniaservice,andthe
secondtypeiscrackingofcopperalloys,suchasadmiraltymetal(C44300).In
copperalloys,SCCcanoccurwithammoniabaseneutralizersthatareadded
tocontrolcorrosion.
Carbonsteelstoragevessels,primarilyspheres,havedevelopedstresscorro
sioncracksinanhydrousammoniaserviceatambienttemperaturebutele
vatedpressure.Inmostcases,crackingwasdetectedbyinspectionbeforeleak
ageorrupture,buttherewereatleasttwocatastrophicfailures.Therehave
beenfewproblemswithsemirefrigeratedstoragevesselsandnodocumented
casesofSCCincryogenicstoragevessels.Theprimarycausesofcrackingare
highstresses,hardwelds,andaircontamination
Tominimizethelikelihoodofcracking,onlylowstrengthsteels,
withamaximumtensilestrengthof483MPa(70ksi),shouldbe
usedinanhydrousammoniaservice.Weldsshouldbepost
weldheattreatedat595C(1100F)orhigher,withamaximum
allowablehardnessof225HB.
Awatercontentofatleast0.2%shouldbemaintainedinthe
ammoniabecausewaterhasbeenfoundtobeaneffectivein
hibitorofcracking.Aircontaminationincreasesthetendencyto
wardcrackingandshouldbeminimized,ifnecessarybythe
addition of hydrazine to the water. With a water content of 10ppm, the oxygen content
shouldbebelow10ppmforsafeoper
ation.Thepermissibleoxygencontentincreasesto100ppm
withawatercontentof0.1%.Regularinspectionofallcompo
nentsinanhydrousammoniaserviceisrecommended.
Crackingofadmiraltymetal(C44300)heatexchangertubes
hasbeenarecurringprobleminanumberofrefiningunitsand
petrochemicalprocessunits.Forexample,ammoniaisoften
usedtoneutralizeacidicconstituents,suchashydrogenchlo
rideorsulfurdioxide,inoverheadsystemsofcrudedistillation
oralkylationunits,respectively.Strippedsourwatercontaining
residualammoniaisusedasdesalterwateratsomecrudedistil
lationunits.Thispracticecausesammoniacontaminationof
theoverheadsystemevenifnoammoniaisaddedintentionally.

Ammoniaisformedfromnitrogencontainingfeedstocksdur
ingcatalyticcracking,hydrotreating,andhydrocrackingopera
tions.Asarule,crackingofadmiraltymetal(C44300)tubesoc
cursonlyduringshutdownswhenammoniacontainingde
positsonthetubesurfacebecomeexposedtoair.Toprevent
cracking,tubebundlesshouldbesprayedwithaverydilute
solutionofsulfuricacidimmediatelyaftertheyarepulledfrom
theirshellsinordertoneutralizeanyresidualammonia.Crack
ingofadmiraltymetal(C44300)tubeshasoccasionallybeen
attributedtotracesofammoniaincoolingwater.
2.1.3.1EstimateoftheRateofAmmoniaCrackingGrowth

AmmoniaStressCorrosionCrackingisaformofstresscorrosion
cracking that commonly occurs in brass tubes in cooling water
servicethathasbeencontaminatedwithammoniaduetobiological
growthsorothercontamination.Thiscrackingcanalsooccurwhen
ammoniaisintentionallyaddedtoprocessstreamsasaneutralizer
by someone unaware of its potential effect on brass tubes. Brass
condensertubescanundergobrittlefractureifbentwhensignificant
ammoniastresscorrosioncrackingispresent.
Ammonia stress corrosion cracking can also affect carbon steel
equipment, but unlike the cracking mechanism on brass which
occurs in an aqueous solution, the cracking of steel equipment
occurs in anhydrous ammonia. Systems with air/oxygen
contaminationalsotendtobeparticularlyvulnerabletothisissue.
Thankfullythough,thereareseveralwaysinwhichammoniastress
corrosioncrackingcanbepreventedinsteelequipment.Firstand
foremost,systemsthathavenotundergonepostweldheattreatment
(PWHT)aremuchmoresusceptible,thusproperPWHTisessential.
Adding a very small amount of water (0.2%) to the anhydrous
ammoniacanalsoinhibitthecrackingofsteel.
When inspecting for ammonia stress corrosion cracking in brass
tubes,someofthebesttechniquestoinvolvetheuseofeddycurrent,
suchaspulsededdycurrenttestingoreddycurrentarraytesting.If
you want to inspect for ammonia cracking in steel tubes, wet
fluorescentmagneticparticletestingisbestforwhereaccesstothe
surface is available; when its not, shear wave ultrasonic testing
tendstoworkbest.

Cupronickelalloysareusuallynotsusceptibletoammoniastress
corrosioncracking,soifallelsefails,upgradingtoanewmaterialis
anotherformofprevention.Austeniticstainlesssteelslikewiseare
resistanttothisformofcorrosion,sousingthemisanotheroption.