Stress Corros|on Crack|ng

Iactors kespons|b|e

arth S ar|kh
ko|| No 932
S1kLSS CCkkCSICN CkACkING

Stress corrosion cracking (SCC) is the unexpected sudden failure of
normally ductile metals subjected to a tensile stress in a corrosive environment,
especially at elevated temperature in the case of metals. SCC is highly chemically
specific in that certain alloys are likely to undergo SCC only when exposed to a small
number of chemical environments. The chemical environment that causes SCC for a
given alloy is often one which is only mildly corrosive to the metal otherwise. Hence,
metal parts with severe SCC can appear bright and shiny, while being filled with
microscopic cracks. This factor makes it common for SCC to go undetected prior to
failure. SCC often progresses rapidly, and is more common among alloys than pure
metals. The specific environment is of crucial importance, and only very small
concentrations of certain highly active chemicals are needed to produce catastrophic
cracking, often leading to devastating and unexpected failure.
The stresses can be the result of the crevice loads due to stress concentration, or can
be caused by the type of assembly or residual stresses from fabrication (e.g. cold
working); the residual stresses can be relieved by annealing.


llg SLress Corroslon Crack

eta|s Attacked
Certain austenitic stainless steels and aluminium alloys crack in the presence
of chlorides, mild steel cracks in the presence of alkali (-oiIer cracking)
and nitrates, copper alloys crack in ammoniacal solutions (season cracking). This limits
the usefulness of austenitic stainless steel for containing water with higher than few
ppm content of chlorides at temperatures above 50 C. Worse still, high-tensile
structural steels crack in an unexpectedly brittle manner in a whole variety of aqueous
environments, especially containing chlorides. With the possible exception of the latter,
which is a special example of hydrogen cracking, all the others display the phenomenon
of subcritical crack growth, i.e. small surface flaws propagate (usually smoothly) under
conditions where fracture mechanics predicts that failure should not occur.

When does SCC occur?
Stress corrosion cracking presents an especially difficult problem, since not only is it
highly localized but it can occur in environments that are merely mildly corrosive to the
material. The damaging concentration of the harmful ions in that environment may be
quite small and difficult to detect and, even in the absence of applied stress, residual
stresses in a structure can often be of a sufficiently high level to cause SCC and failure
in service.

llg CrowLh raLe of SCC cracks
ln a glven slLuaLlon Lhe Llme of exposure needed Lo cause SCC fallure depends on
Lhe sLress lnLenslLy aL any preexlsLlng or developed crack Llp 1he concenLraLlon
of sLress aL Lhe Llp of a sharp crack or flaw can be quanLlfled ln Lerms of Lhe SLress
lnLenslLy lacLor k lL deLermlnes Lhe growLh raLe of SCC cracks for a speclflc alloy
envlronmenL comblnaLlon CaLasLrophlc fallure of componenL wlll occur when Lhls
facLor reaches a crlLlcal value Lhe lracLure Loughness of Lhe maLerlal k1C 1hls
enables Lhe deLermlnaLlon of allowable defecL slze ln deslgn Lo avold fallure under
glven loadlng condlLlons
8elow a Lhreshold value of k1 called k1SCC growLh of a crack by SCC ls noL
expecLed buL above Lhls value Lhe lnlLlal SCC growLh raLe lncreases wlLh
lncreaslng k1 called sLage 1 cracklng
ln sLage 2 Lhe crack growLh raLe ls lndependenL of k1 and depends lnsLead on Lhe
corroslve envlronmenL and LemperaLure uurlng sLage 2 growLh k1 conLlnuous Lo
lncrease and Lhls leads Lo Lhe rapld acceleraLlon of Lhe crack ln sLage 3 and flnal
fasL fracLure when k1 reaches k1C whlch ls Lhe fracLure Loughness of Lhe maLerlal
1he hlgher Lhe value of k1SCC under glven condlLlons Lhen Lhe greaLer ls Lhe
expecLed SCC reslsLance buL some maLerlals do noL appear Lo have a Lhreshold
reslsLance

1hermodynam|cs of Stress Corros|on Crack|ng
1he Lhermodynamlcally condlLlons for anodlcally asslsLed SCC are LhaL
dlssoluLlon or oxldaLlon of Lhe meLal and lLs dlssoluLlon ln Lhe elecLrolyLe musL be
Lhermodynamlcally posslble and LhaL a proLecLlve fllm such as an oxlde or salL
musL be sLable 1he flrsL condlLlon becomes a requlremenL because wlLhouL
oxldaLlon crack advance by dlssoluLlon would noL occur 1haL a process ls
conLrolled by anodlc dlssoluLlon does noL lndlcaLe LhaL Lhe LoLal crack exLenslon ls
Lhe sum of Lhe LoLal number coulombs of charge exchanged aL Lhe crack Llp
1here are crack advance processes ln whlch Lhe crack advance ls conLrolled by
anodlc dlssoluLlon buL ln whlch Lhe LoLal crack lengLh ls greaLer Lhan LhaL whlch
can be accounLed for Lhe LoLal charge Lransfer Powever lL ls lmporLanL Lo noLe
LhaL lf Lhe brlLLle crack advancemenL ls lnlLlaLed and conLrolled by anodlc
dlssoluLlon Lhe crack growLh raLe wlll be zero lf Lhe anodlc currenL denslLy ls zero
and wlll lncrease wlLh lncreaslng currenL denslLy
1he Lhermodynamlc requlremenL of slmulLaneous fllm formaLlon and oxldaLlon
can be undersLood from Lhe dlagram shown ln flg ln whlch Lhe raLlo of corroslon
currenLs from Lhe walls relaLlve Lo Lhe crack Llp ls Lhe crlLlcal parameLer 1hls raLlo
musL be subsLanLlally less Lhan 1 for a crack Lo propagaLe CLherwlse Lhe crack
wlll blunL or Lhe crack Llp soluLlon wlll saLuraLe Crack lnlLlaLlon can also be
conLrolled by Lhls raLlo because a plL wlLh a hlgh wall corroslon raLe wlll broken
fasLer Lhan lLs peneLraLlon resulLlng ln general corroslon raLher Lhan crack
growLh lL ls generally belleved LhaL Lhe acLlvlLy of Lhe crack walls relaLlve Lo Lhe
crack Llp ls a consequence of Lhe greaLer dynamlc sLraln aL Lhe Llp Lhan along Lhe
walls

llg SchemaLlc dlagram of sLress corroslon crack showlng lmporLanL LransporL and
corroslon reacLlons

Intergranu|ar Stress Corros|on Crack|ng
MaLerlal chemlsLry and mlcrosLrucLure effecLs on lnLergranular SCC can be dlvlded
lnLo Lhe followlng Lwo caLegorles graln boundary preclplLaLlon and graln
boundary segregaLlon Craln boundary preclplLaLlon lncludes carblde
preclplLaLlon ln ausLenlLlc sLalnless sLeel and nlckel based Alloys whlch causes
depleLlon of chromlum ad[acenL Lo Lhe graln boundary and lnLermeLalllc
preclplLaLlon of Alumlnlum Alloys whlch are anodlcally acLlve Craln boundary
segregaLlon of lmpurlLles such as phosphorous carbon and sulpher can produce
a graln boundary LhaL ls upLo 30 lmpurlLy wlLhln 12 nm Lhlck reglon 1hese
lmpurlLles can alLer Lhe corroslon and mechanlcal properLles of graln boundary
and Lherefore cause cracklng by anodlc dlssoluLlon and perhaps mechanlcal
fracLure

llg CausLlc SCC ln Lhe PAZ of a Lype 316L sLalnless sLeel naCP reacLor vessel
Cracks are branchlng and lnLergranular

1ransgranu|ar Stress Corros|on Crack|ng
numerous meLallurglcal facLors affecL Lransgranular SCC for example crysLal
sLrucLure anlsoLropy graln slze and shape dlslocaLlon denslLy and geomeLry
yleld sLrengLh composlLlon eLc some of Lhelr effecLs on Lransgranular SCC are
also relaLed Lo Lhe corroslon behavlor of Lhe alloy whlch can be undersLood from
poLenLlalpP dlagrams or polarlzaLlon curves
Alloylng effecLs on a sllp plane on a meLallurglcal facLor ln Lransgranular SCC
lanar sllp occurs ln alloys wlLh low sLacklng faulL energy alloys exhlblLlng long
range or shorL range orderlng ln Lhls mechanlsm Lhe passlve fllm ls rupLured by
Lhe emergence of a sllp sLep A number of crack growLh processes were suggesLed
based on a planer sllp locallzed processes llke conLrol of crack advance solely by
anodlc dlssoluLlon of Lhe sllp plane brlLLle fracLure of Lhe corroslon producL or
Larnlsh fllm formed along Lhe locallzed corroslon paLh 1he planar sllp concepL of
Lransgranular SCC appears conslsLenL wlLh a number of observaLlons such as
alloylng and sLraln raLe effecLs
1he laLesL concepL whlch has recelved conslderable aLLenLlon ls Lhe one ln whlch
a rapld crack advance LhaL beglns ln a brlLLle fllm aL Lhe crack Llp lnduces cleavage
fracLure of Lhe ducLlle maLerlal ahead of Lhe crack Llp 1hese lnclude dealloyed
layer oxlde nlLrlde or carblde A dealloyed layer acLlng as a cleavage crack
lnlLlaLor ls suggesLed for brass coppergold and lronchromlumnlckel alloys lf
Lhls concepL ls supporLed by fuLure research Lhe relaLlve reacLlvlLy of Lhe alloylng
elemenLs wlll prove Lo be a key meLallurglcal facLor ln Lhe Lransgranular SCC of
maLerlals


llg 1ransgranular SCC 304 SLalnless SLeel 8ase 308 SLalnless SLeel Weld ln
aqueous chlorlde aL 93C





Var|ous Iactors Inf|uenc|ng Stress Corros|on Crack|ng

O lnfluence of elecLrode poLenLlal
1he elecLrochemlcal poLenLlal of Lhe alloy can have a marked lnfluence on Lh
Lendency for SCC Lo occur lor hydrogen embrlLLlemenL of hlgh sLrengLh sLeel
a more negaLlve poLenLlal wlll Lend Lo lncrease Lhe raLe of hydrogen evoluLlon
and Lhereby Lhe suscepLlblllLy Lo hydrogen embrlLLlemenL lL ls less obvlous
how lL happens buL more poslLlve poLenLlals Lhan Lhe Lyplcal free corroslon
poLenLlal may also lncrease Lhe enLry of hydrogen


O lasLlc ueformaLlon
1he few avallable daLa show LhaL plasLlc deformaLlon may exerL a Lwo fold
lnfluence on Lhe raLe of sLress corroslon cracklng ln some lnsLance lncreaslng
and ln anoLher decreaslng lL 1he naLure of sLress corroslon cracklng may also
be changed LranscrysLalllne Lo lnLercrysLalllne or vlce versa

O lnfluence of sLresses
1he lnfluence of sLresses ls dependenL on Lhe naLure of corroslve envlronmenL
SLresses lrrespecLlve of Lhelr naLure lncrease Lhe raLe of corroslon ln acld
envlronmenLs and Lhere ls llnear relaLlonshlp beLween Lhe lncrease of raLe of
corroslon and lncrease of sLress CerLaln excepLlons can be menLloned
l 8olllng of lead ln PCL
ll 177 grade sLalnless sLeel ln PCL aL elevaLed LemperaLure
lll Cold rolled pure alumlnlum ln 1n soluLlon of PCL


O lnfluence of 1emperaLure
1he raLe of corroslon conLlnuously and lnLenslvely lncreases wlLh lncrease ln
LemperaLure of envlronmenL

O lnfluence of Slze lacLor
1he decrease of area Lo volume raLlo sLressed corrodlng speclmens leads Lo a
sharp decrease of Lhe raLe of sLress corroslon cracklng vlz Armco lron ln 30
bolllng soluLlon of ammonlum nlLraLe magneslum alloy (Al 63 Zn 1 Mn
02) ln a soluLlon of sodlum chlorlde and poLasslum chromaLe Al+7 Mg
alloy ln a soluLlon of naCl

O lnfluence of Alloylng LlemenL
1he degree of lnfluence of alloylng elemenL on SCC depends upon Lhe naLure
of alloylng elemenL and envlronmenL prellmlnary heaL LreaLmenL and
mechanlcal LreaLmenL lor example sLress corroslon raLe lncreases as Lhe
carbon conLenL ln sLeel ls lncreased upLo 043 buL furLher lncrease ln Lhe
carbon conLenL decreases Lhe raLe of sLress corroslon

keferences
wwwnaLlonalphyslcallaboraLorycouk
wwwcorroslondocLorsorg
wwwwlklpedlacom
Corroslon Lnglneerlng 8y Mars C lonLana
lnLroducLlon Lo LlecLromeLallurgy Corroslon 8y Sharan and naraln
ASM Pandbook no 13 corroslon