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WhatisCausticEmbrittlement?

Definitionfrom
Corrosionpedia
CausticEmbrittlement
DefinitionWhatdoesCausticEmbrittlementmean?
Causticembrittlementisaphenomenonthatoccursinboilerswherecausticsubstancesaccumulateinboiler
materials.Italsocanbedescribedasthecrackingofrivetedmildsteelboilerplates.Thisoccursat
temperaturesof200250Casaresultoflocaldepositionofconcentratedhydroxide.
Causticembrittlementfocusesonthestressedpartsoftheboiler,includingcracks,bends,rivetsandjoints.
Residualsodiumcarbonate,whichisusedforthesofteningprocess,undergoeshydrolysis,formingsodium
hydroxideathighpressuresandtemperatures.
Causticembrittlementisalsoknownasstresscorrosioncracking.

CorrosionpediaexplainsCausticEmbrittlement
Therearemanycausesofcausticembrittlement,includingthecombinedactionofthefollowingthree
components:
Asusceptiblematerial
Agivenchemicalspecies
Tensilestress
Sodiumhydroxide(causticsoda)preventsscalingwhenaddedtotheboilerwater.Thepresenceofalkaliin
thecrevices,foundaroundtherivetheadsandotherhotspots,combinedwithfabricationstressaroundrivet
holes,causescracksinthesteelboilershellsandtubeplates.
Thealkalinewaterenterstheminuteholesandcracksbycapillarityactionontheinterioroftheboiler.The
waterthendiffusesoutofthecracks,leavingbehindhydroxidesaltsthataccumulatewhenmorewater
evaporates.Thehydroxidethenattacksthesurroundingmaterialoftheboileranddissolvesironassodium
ferrite.
ThiscorrosionathighpHlevelsproduceshydrogen,whichattacksthecrystalstructureofiron,makingit
hardandbrittle.Thisishighlydangerousbecausethetubecanthenfailattheboiler'snormaloperating
temperature.
Causticembrittlementcanbepreventedthroughseveralmethods,including:
Controllingthetemperatureandpotential
Controllingthestresslevelsandhardness
Useofmaterialsthatdonotcrackwhenusedingivenenvironments
Avoidingalkaliwherenecessary
Replacingsodiumcarbonateswithsodiumsulphatesassofteningreagents

Addinglignin,tanninorsodiumsulphatethatblockshairlinecracksaswellaspreventinginfiltrationof
sodiumhydroxideintotheareas
ByNemanjaPavlovic,July1,2016
Takeaway:Differenttypesofcorrosioncanhavesignificantlydifferenteffectsonmetalconstruction
materials.Exercisecarewhendesigning,constructingandmaintainingstructuresthatareproneto
corrosion.

Source:CeciliaLim/Dreamstime.com
Modernconstructionmaterialshaveanumberofwelldefinedmechanicalpropertiesthatcantellusalot
abouttheircharacteristicsandbehaviorwhenusedinconstruction.However,thestoryisfarfromcomplete
becauseofnewlydevelopedmaterialswhosebehaviorisstillunknownandbecausewediscovernew
damagemechanismsaswecreatemoreandmoreadvancedapplicationswithnewenvironmentsand
modesofoperation.
Mostofthesepropertiesareexplainedonamicroscopiclevel,buttheirtruenatureisbestunderstoodona
macroscopiclevel,throughnumeroustestsand,unfortunately,experience.Thesetestsarecommonly
performedusingstandardizedtestspecimensandtestequipmentthatgiveusaccurateestimatesofvarious
characteristicswedefine,suchasmaterialstrength,toughness,hardness,resilienceandductility.Allof
thesepropertiesaremutuallydependent,andonlyhaveuseinhelpingusdescribethedifferentqualitiesof
amaterialtheyarenotseparate,independentmechanicalproperties.Entercompositematerials,andthe
wholestorybecomesevenmorecomplicated.(Foraquicklookatcomposites,seeGalvanicCorrosionof
MetalsConnectedtoCarbonFiberReinforcedPolymer.)
Oneoftheoldestpropertieswedefinedisthatofthematerialsstrength,whichcomesintwoflavors:
compressiveandtensilestrength.Tensilestrengthisoneofthemostimportantmechanicalpropertiesfor
anysortofmodernconstruction,asitdefinesthebreakinglimitofamaterialundertensilestress(anaspect
towhichmostmaterialsaremorevulnerablethantotheeffectofcompressiveforces).Withoutanaccurate
knowledgeofthisvalue,wecannotevendreamofdesigningastructurethatwouldbewithina
predeterminedmarginofsafetywithadequatereliability.

Todeterminehowcorrosionaffectstensilestrength,weneedtoobservetwopartsoftheproblem:
Thenatureofthemechanicalproperties
Theinfluenceofcorrosiononsaidproperties

TheNatureoftheMechanicalPropertiesofMetals
Most,ifnotallpropertiesdefinedsofarareobservedinsteels,aluminumalloysandothermetalscommonly
usedinconstructionandengineering.Forthatreason,itiseasiesttoexplainthesemechanismsandtheir
interactionwithatypicalexample,suchasconstructionsteel.
Therearetwolevelsofscalethatplayarolehere:thecrystallatticeofametal,comprisedofanumberof
atomsarrangedinapattern(usuallyacube,butotherpatternsexist),andonagrainlevel,acrystalline
structurecomprisedofalargenumberofindividuallattices.Thesegrainscanhavevaryingsizes,often
downtothemicroscopiclevel.
Itisnotnecessarytospendtoomuchtimeheredebatingthebasicatomiclevelofthisproblem:sufficeto
saythattheselatticesarenotperfect.Sometimesatomsaremissing,ortheyaresubstitutedwithother
atoms(substitutionaldefect)orthereareatomsstuckinsideofthelattice(interstitialdefect),allofwhich
havedifferentandsignificanteffectsonthepropertiesofthemetal.Infact,theseimperfectionsareexactly
whatmakeitpossibleforustoinfluencethecharacteristicsofametalbyalloying,andbymechanicaland
thermalprocessing,buttheseeffectsareindividuallylessvisiblethanonthegrainlevel.Thedefects
mentionedherearethesocalledpointdefects,whileotherlevels,suchasline,planarorbulkdefectsare
alsoalwayspresentinsomemeasure.
Themicrostructureofamaterialisfarfromhomogenous,evenonmicroscopiclevel.Crystallinedefectscan
allowtheflowofthematerial,ortrapitandbeanobstacletocrackpropagationanddeformation,andbe
responsibleforresidualandinternalstresses.Besidesthechemicalcompositionofamaterial,these
inhomogeneouslatticeandgrainstructuresareresponsibleforthewidevarietyofpropertieswegetfrom
somematerials.
Itwouldbevirtuallyimpossibletostudyandrecordeverysinglelatticeinametalandtrytoestablishits
propertiesbasedonthem.Forthatreason,itismoreprudenttoobservethemicrostructureonagranular
level.Thesegrainsaremultifaceted,withdifferentpossibleshapes,internalstructureandsize,allofwhich
influencethematerialsmechanicalpropertiesinacertainway.Generally,thesmallerthegrains,thebetter
themechanicalpropertiesthatisthereasonwhy,asarule,highstrengthsteelshaveaveryfine
microstructure.
Tensilestrengthbydefinitionistheresistanceofmaterialtobreakingundertension.Intermsof
mechanics,thismeansthattensilestrengthisthestressvaluethatamaterialcanendurebeforeitbreaks.
Therearedifferentmodesofmaterialbreakingdependingonthetypeofmaterial,thefailurecanbeductile
wherefirstthematerialexperiencesplasticdeformationorbrittlefailurewithnopriordeformation.
Onanatomiclevel,tensilestrengthisthestrengthoftheattractiveforcesbetweentheatomsandlattices
thatopposeanyoutsideforcesthataffectthematerialinthedirectionoftheattackofthesaidforces.

InfluenceofCorrosionontheStructureofMaterials

Asiswellestablished,corrosionisachemicalorelectrochemicaldegradationofmaterial,causedbythe
interactionofthematerialwiththeenvironment.Inthecaseofsteelsthisusuallystemsfromapresenceof
oxygenandanelectrolyte,suchaswaterorsaltwater,whichareinevitableoccurrencesinamarine
environmentorinwaterpipelines.(ReadhowMarineStructuresCreateUniqueChallengesforThirdParty
Inspectors).
Intheory,coatings,sacrificialanodesandpassivationcanreduceorcompletelynegatecorrosion,but
unfortunately,inanyreallifescenario,numerousotherfactors,suchastemperature,variableloads,
vibrationandmicrobialactivitygreatlyreducetheeffectivenessoftheseprotectionmethods.Theeffectsof
corrosiononcrackpropagationaresignificant.(Foranindepthexample,readthearticleCorrosionFatigue
ofWeldedJointsonMarineOffshoreStructures.)
Theeffectofcorrosiononmechanicalpropertieswillbeshownonuniformandpittingcorrosion,someofthe
mostcommonmechanismsthatwedealwithonadailybasis.Uniformcorrosion,asthenameimplies,
spreadsuniformlyovertheentiresurfaceofthepartinquestion.Pittingcorrosionisahighlylocalized
corrosionwhereaminutebreakageofaprotective(passive)layerleadstothecreationofapitwhere
localizedgalvaniccorrosionoccursthroughaverycomplexcorrosionmechanism,evenifthesurfacelayer
wasresealed.
Inthecaseofuniformcorrosion,assessingitsinfluenceonthematerialsstructuralstrengthis
straightforward.Oneshouldestablishthereductionofthethicknessandtheweightlossoftheplateorbeam
inquestion,andcalculatethestressforagivenloadforanew,reduced,crosssectionofthesteelmember.
Thematterisfarmorecomplicatedforlocalizedcorrosion,wherethelocalizedstressfieldsplayamuch
largerroleanddirectlyaffectthetensilestrengthofthematerialitself.
Tobetterillustratethis,acasestudydonebyNakai,Matsushita,andYamamotoonaholdframeofa14
yearoldbulkcarriershowedthat:
Adecreaseofnominaltensilestrengthandoftotalelongationwasafunctionofthethickness(depthof
pits)ofthecorrodedlayer.Withthelossofthemembersthicknessduetocorrosion,tensilestrength
decreasedgradually,whilethemaximumelongationdecreasedinasteeperfashion.Nominaltensile
strengthisnotthesameastheultimatetensilestrengthoneisapropertyofastructureorits
component,andtheotherisapropertyofamaterial.Inthiscase,nominalstrengthreferstothe
maximumloadovertheoriginalcrosssectionarea(whichisobviouslyreducedduetocorrosion).
Thisreductioninmaximumloadcarryingcapacitywasobservedtobe2.5timesgreaterinamemberwith
pittingcorrosioncomparedtoamemberwithuniformcorrosion.
Whenexaminingsmallspecimens,themaximumallowedtensileloadcouldstillbepredictedbyusingthe
ultimatestrengthofthematerial(multiplyingthecrosssectionbytheultimatetensilestrength).
Whenwidespecimens(plates)areused,stressconcentrationscausedlocalplasticdeformationsand
localfractureinitiationintheimmediatevicinityofthelargerpits.Thismeansthatthestressthresholdfor
crackinitiationforwidespecimensislowerthanforsmallspecimens.
Besidestheseeffectsontensilestrength,pittingcorrosionalsohadagreaternegativeimpactonthe
bucklingstrengthofamembercomparedtouniformcorrosion.
Ontheotherhand,examinationofcorrodedreinforcingsteelbarsdonebyAlmusallamshowedasignificant
reductionofductility,andthespecimenswithmorethan12.6%showedconsiderablebrittlebehavior
comparedtothecontrolspecimens.Inaddition,thesebarsshowedreducedelongation.Afteracertainpoint

(whenmorethan40%ofthematerialiscorroded),theserebarsshowedpreferentialcorrosion,witha
relativelyshortsectionshowingthinningandnotchformation,butthesecouldbeattributedtocracked
concreteandotherenvironmentalfactorsnotdirectlyrelatedtocorrosion.Thisreductioninrebarthickness
significantlyreducesitsloadcarryingcapacity,whilethebrittlemodeoffailuremakesthesituationfarmore
dangerousduetothemuchfasterpropagationofcracksinsuchamaterial.

TensileStrength,DuctilityandBrittleness
Whilecorrosionhasamarginaleffectontheultimatetensilestrengthofamaterial,thereisastrong
correlationbetweencorrosionandareductioninductilityandanincreaseinbrittlenessofthematerial,which
inturncanchangethefailuremodefromaductiletoamuchmoredangerousbrittlefailure.Inaddition,
reducedcrosssectionandstressconcentrationscausedbycorrosioncangreatlyinfluencetheloadcarrying
capacityoftheparticularmemberandthestructureasawhole.
Differenttypesofcorrosioncanhavesignificantlydifferenteffectsonastructuralmember,whichsadly
meansthatwecanonlyexaminetheseeffectsonacasebycasebasis,significantlyslowingdownour
understandingoftheproblemsathand.Thereisasignificantdangerinleavingevenseeminglybenign
corrosionunchecked,socareshouldbetakenwhendesigning,constructingandmaintainingstructuresthat
arepronetocorrosion.