CkIDA1ICN

CxldaLlon generally refers Lo an elecLron produclng reacLlon buL Lhls

Lerm can be employed Lo deslgnaLe Lhe reacLlon beLween a meLal and
alr or oxygen ln Lhe absence of waLer or an aqueous phaseScale
formaLlonLarnlshlng dry corroslon may be used Lo descrlbe Lhls
phenomenon
8ased on Lhe Lemp employed for any process oxldaLlon may classlfy ln
Lo Lwo dlsLlncL Lypes
O ow Lemp oxldaLlon
O lgh Lemp oxldaLlon
Many meLals when exposed Lo alr even aL room Lemp forms surface
compounds whlch may be oxldes or oLher compounds dependlng
upon Lhe conLamlnaLlon of alr 1he formaLlon of compound Lake place
because Lhe meLal ls noL sLable as such ln Lhe envlronmenL lL Lends Lo
undergo a reacLlon Lo reach a sLable form 1hls may be Lermed as /ow
temp oxidotion
1he Lerm hiqh temp oxidotion refers Lo maLerlal degradaLlon aL
LemperaLures hlgher Lhan Lhe amblenL Lemp when exposed Lo
corroslve envlronmenLs ow hlgh ls Lhe LemperaLure ls a relaLlve
Lerm whlch varles from meLal Lo meLal and also ln some on Lhe Lype of
envlronmenLs
A plece of lron and mlld sLeel forms an oxlde layer on Lhe surface when
exposed Lo alr lL Lakes from a few hours Lo few days Lo form oxlde
layer dependlng upon Lhe Lype of envlronmenL 1he raLe of Lhe same
reacLlon of Lhe oxlde formaLlon lncreases many folds lf Lhe sample ls
exposed Lo a same aLmosphere ln an even aL a Lemp much hlgher Lhan
Lhe room LemperaLure lL ls because of Lhe lncrease ln Lhe raLe of
reacLlon aL hlgher LemperaLure many meLals and alloy have a Lendency
Lo form sLable producL and hence undergo degradaLlon 1he maLerlal
degradaLlon due Lo Lhe reacLlon wlLh envlronmenL lncreases many folds
wlLh lncrease ln LemperaLure
1here ls need Lo sLudy hlgh LemperaLure oxldaLlon Lo know
l ow fasL meLal reacL wlLh envlronmenL aL hlgh LemperaLure
ll WhaL ls Lhe mechanlsm of Lhe reacLlon?
lll ow corroslve ls Lhe envlronmenL
lv ow Lo conLrol Lhe reacLlon or how Lo proLecL meLal from
degradaLlon and flnally
v ow Lo selecL maLerlal for such hlgh LemperaLure appllcaLlons
CxldaLlon ls Lhe mosL lmporLanL hlgh LemperaLure corroslon reacLlon
ln mosL lndusLrlal envlronmenLs oxldaLlon ls ofLen one of Lhe reacLlons
lrrespecLlve of Lhe predomlnanL mode of corroslon ln facL alloys ofLen
rely upon Lhe oxldaLlon reacLlon Lo develop a proLecLlve oxlde layer Lo
reslsL corroslon aLLack 1he oxldaLlon behavlor of maLerlals aL levaLed
LemperaLures became of paramounL lmporLance slnce lL ls of lnLeresL
ln many domalns of maLerlal sclence and lndusLrlal englneerlng eg
hlgh LemperaLure processes ln chemlcal lndusLrles or meLal producLlon
and fabrlcaLlon lL ls now essenLlal Lo conLrol hlgh LemperaLure
oxldaLlon and Lherefore Lo lnvesLlgaLe Lhe klneLlcs of Lhe oxlde fllm
growLh


L|ectro chem|ca| aspects of Cx|dat|on
1he chemlcal formula for Lhe reacLlon of meLal M and oxygen gas C
2
Lo
form Lhe oxlde MC may be wrlLLen as
M + 1/2C

MC
CxldaLlon ls an elecLrochemlcal process and lnvolves Lwo parLlal
speclally separaLed processes
M M
2+
+ 2
e
(meLal oxldaLlon aL meLal scale lnLerface)
1/2C
2
+ 2
e
C
2
(oxldanL reducLlon aL scale gas lnLerface)
M + 1/2C
2
MC (overall)
1hls reacLlon can be consldered as a speclal case of heLerogeneous
reacLlon 1he reacLlon paLh and Lhe oxldaLlon behavlor may be depend
on a varleLy of facLors and Lhe reacLlon mechanlsms ofLen prove Lo be
complex
A schemaLlc cross secLlonal vlew of a growlng oxlde scale ls shown ln
flgure 1he overall oxldaLlon process can be subdlvlded ln Lo several
sLeps
l ellvery of oxldanL Lo Lhe scalegas lnLerface vla mass Lransfer ln
Lhe gas phase
ll lncorporaLlon of oxygen lnLo Lhe oxlde scale
lll ellvery of reacLlng meLal from Lhe alloy Lo Lhe alloyscale
lnLerface
lv lncorporaLlon of meLal lnLo Lhe oxlde scale
v 1ransporL of meLal and/or oxygen Lhrough Lhe scale
When a meLal wlLh a clean surface ls exposed Lo oxygen gas Lhe lnlLlal
oxldaLlon phase can be dlvlded lnLo Lhe followlng Lhree sLages
SLarLlng wlLh a clean surface Lhe lnlLlal sLep ln Lhe meLaloxygen
reacLlon ls Lhe adsorpLlon of Lhe gas on Lhe meLal surface As Lhe
reacLlon proceeds lndlvldual separaLed oxlde nuclel are formed on Lhe
surface whlch grows laLerally Lo form a conLlnuous oxlde fllm on Lhe
meLal surface 1hus Lhe oxlde fllm separaLes Lhe meLal from Lhe gas
and Lhe reacLlon mechanlsm changes compleLely 1he reacLlon can only
proceed by a solld sLaLe dlffuslon of one or boLh of Lhe reacLanLs
Lhrough Lhe oxlde fllm numerous mechanlsms of reacLlon have been
consldered Lo accounL for Lhe many LemperaLure dependenL oxldaLlon
phenomena observed Lhe many models dlffer ln Lhelr assumpLlons
abouL Lhe raLe deLermlnlng processes 1he LransporL mechanlsm
Lhrough Lhe oxlde fllm Lhe drlvlng force for Lhese LransporL of
reacLanLs due Lo elecLrlc flelds ln or across Lhe fllm whereas for Lhlck
fllms Lhe oxldaLlon klneLlc deLermlned by Lhe chemlcal poLenLlal
gradlenL across Lhe scale lor a parLlcular meLal Lhe reacLlon
mechanlsm wlll ln general be a funcLlon of surface characLerlsLlcs of Lhe
sample elapsed Llme of reacLlon and gas composlLlon and pressure
When Lhe large varlaLlon of Lhe properLles of dlfferenL meLals and Lhelr
oxldes are also consldered
Cx|dat|on k|net|cs
1he mosL lmporLanL parameLer of Lhe meLal oxldaLlon from Lhe
englneerlng polnL of vlew ls Lhe reacLlon raLe 8aLe equaLlon whlch are
commonly classlfled as ogarlLhmlc parabollc cublc and llnear 1hey
represenL only llmlLlng and ldeal cases evlaLlons and lnLermedlaLe
raLe equaLlons are ofLen encounLered ln many cases lL ls dlfflculL or
even lmposslble Lo verlfy Lhe valldlLy and Lhe correcLness of Lhe varlous
models and parameLers lnvolved ln Lhe equaLlons derlved lL can be
dlfflculL Lo flL raLe daLa Lo slmple raLe equaLlons ln Lhe followlng a
selecLlon of Lhe mosL lmporLanL klneLlc raLe laws for hlgh LemperaLure
oxldaLlon wlll be brlefly descrlbed lL ls characLerlsLlc of Lhe oxldaLlon of
a large number of meLals aL low LemperaLure (400
o
c) LhaL Lhe reacLlon
can be descrlbed by logarlLhmlc raLe equaLlons
|near rate |aw
1he oxlde reacLlon producL ls generally reLalned on Lhe meLal surface
and so Lhe raLe of oxldaLlon ls usually measured and expressed as
welghL galn per area 1he slmplesL emplrlcal relaLlonshlp ls Lhe llnear
law
W k

L
Where W welghL galn per area
1 Llme
k

llnear raLe consLanL

llnear oxldaLlon ls Lhe characLerlsLlc of meLal for whlch a porous or
cracked scale ls formed so LhaL Lhe scale does noL represenL a dlffuslon
barrler beLween Lhe Lwo reacLanLs na k oxldlze llnearly and have
oxlde Lo meLal volume raLlo less Lhan 1 Slmllarly LanLalum and
columblum oxldlze llnearly and have oxlde Lo meLal volume raLlo of
abouL 23
1he llnear raLe consLanL represenLs Lhe raLe aL whlch some molecular
dlssoclaLlon or some oLher reacLlon sLep aL Lhe lnLerface ls conLrolllng
Lhe LoLal reacLlon raLe

Janger's theory (parabo||c rate |aw)
ln 1933 C Wagner showed LhaL Lhe ldeal lonlc dlffuslon conLrolled
oxldaLlon of pure meLals should follow a parabollc oxldaLlon raLe flaw
W
2
k

L + C
Where W welghL galn per unlL area
1 Llme
k

parabollc raLe consLanL

meLals demonsLraLlng a parabollc oxldaLlon raLe yleld a sLralghL llne
when Lhe ls ploLLed as W
2
v/s Llme lL ls a form of non sLeady sLaLe
dlffuslon conLrolled reacLlons 1hls equaLlon can be derlved by
assumlng LhaL an oxlde layer of a specles wlLh flxed concenLraLlon aL
Lhe Lwo scale boundarles 1he lonlc dlffuslon flux ls lnversely
proporLlonal Lo Lhe Lhlckness of x" of Lhe dlffuslon barrler and Lhe
change ln scale Lhlckness or welghL ls llkewlse proporLlonal Lo Lhe lonlc
dlffuslon flux
lor Lhe oxldaLlon of le Co nl and Cu where Lhe condlLlons are
saLlsfled Lhe calculaLed and Lhe observed parabollc raLe consLanLs are
ln good agreemenL 1hls law ls usually assoclaLed wlLh Lhlck coherenL
oxldes 1he fallure of experlmenLal daLa Lo saLlsfy parabollc raLe
dependence for a Lhlck coherenL scale lndlcaLes LhaL Lhe morphologlcal
compllcaLlons are prevenLlng Lhe ldeal parabollc condlLlons


ogar|thm|c rate |aw
W k
e
log(CL + A)
Where W welghL galn per unlL area
k
e
CA are consLanLs
1he relaLed lnverse logarlLhmlc oxldaLlon raLe law
1/W C k
l
log L
Where C k
l
are consLanLs
1he logarlLhmlc oxldaLlon behavlor ls generally observed wlLh Lhln
oxlde layers aL low LemperaLures Alumlnlum copper lron and some
oLher meLals oxldlze ln Lhls manner aL amblenL or sllghLly elevaLed
LemperaLure lL ls generally consldered LhaL logarlLhmlc oxldaLlon
occurs from Lhe effecL of elecLrode poLenLlal gradlenL wlLhln very Lhln
oxlde layers ln asslsLlng lonlc LransporL across Lhe scale
Cub|c rate |aw
under speclflc condlLlons some meLals appear Lo oxldlze accordlng Lo a
cublc raLe law
W3 k
c
L + C
Where k
c
C are consLanLs
usually such behavlor ls resLrlcLed Lo shorL exposure perlods lor Lhe
oxldaLlon of zlrconlum and halfnlum apparenL cublc raLe laws have
been explalned as a comblnaLlon of dlffuslon llmlLed scale formaLlon
and oxygen dlssoluLlon lnLo Lhe meLal
A llnear oxldaLlon raLe ls Lhe deslrable as welghL galn lncreases aL a
consLanL raLe wlLh Llme arabollc and logarlLhmlc oxldaLlon raLes are
more deslrable for alloys used ln hlgh LemperaLure oxldlzlng
envlronmenLs MaLerlals LhaL logarlLhmlcally reach an apparenL llmlLlng
fllm Lhlckness

o|e of d|ffus|on |n h|gh temperature ox|dat|on
lgh LemperaLure oxldaLlon ls baslcally Lhe reacLlon of a meLal wlLh
oxygen Lo form an oxlde 1here are varlous sLages whlch lead Lo Lhe
formaLlon of an oxlde scale 1hln layer reglme ls LhaL ln whlch oxldaLlon
occurs aL low LemperaLures under Lhese condlLlons dlffuslon ls
generally noL consldered A more approprlaLe Lerm ls Lhe mlgraLlon of
lron As ln Lhe case of cabera moLL Lheory absorpLlon of oxygen
resulLs ln creaLlng a fleld whlch ls enough Lo cause of Lhe mlgraLlon of
cauLlon from Lhe meLal surface Such a process ls resLrlcLed Lo only a
few monolayers AL hlgh LemperaLures Lhe phenomenon of monolayer
formaLlon ls lnslgnlflcanL 1he lnlLlal layer form Loo fasL Lo record lLs
sequence of formaLlon and Lhe whole process of oxldaLlon depends
upon how Lhls monolayer grows Lo form Lhlck layer 1he Lhlck layer
reglme ls governed by Wanger's Lheory of oxldaLlon buL Wangor's
Lheory requlres an ldeal sysLem where Lhe scale ls almosL
sLochlomeLrlc lL ls adherenL and pore free Also Lhe dlffuslon ls
expecLed Lhrough laLLlce dlffuslon or bulk dlffuslon only owever ln
many pracLlcal oxlde scale formaLlon Lhe shorL clrculL dlffuslon ls more
lmporLanL Lhan Lhe bulk dlffuslon
AnoLher lmporLanL aspecL of dlffuslon ln hlgh LemperaLure oxldaLlon ls
Lo deLermlne Lhe mechanlsm of oxldaLlon le whlch of Lhe Lwo specles
caLlon or anlon ls Lhe raLe deLermlnlng sLep lmlLaLlon of convenLlonal
marklng experlmenLs Lo Lhe laLesL Lracer sLudy can be used Lo measure
Lhe dlffuslon of domlnanL lon
CCCSICN LVLN1ICN
8y reLardlng elLher Lhe anodlc or caLhodlc reacLlons Lhe raLe of
corroslon can be reduced 1hls
can be achleved ln several ways

1 Cond|t|on|ng the Meta|
1hls can be subdlvlded lnLo Lwo maln groups
(a) cootloq tbe metol ln order Lo lnLerpose a corroslon reslsLanL coaLlng
beLween meLal
and envlronmenL 1he coaLlng may conslsL of
(l) anoLher meLal eg zlnc or Lln coaLlngs on sLeel
(ll) a proLecLlve coaLlng derlved from Lhe meLal lLself eg alumlnlum
oxlde on
anodlsed" alumlnlum
(lll) organlc coaLlngs such as reslns plasLlcs palnLs enamel olls and
greases
1he acLlon of proLecLlve coaLlngs ls ofLen more complex Lhan slmply
provldlng a barrler
beLween meLal and envlronmenL alnLs may conLaln a corroslon
lnhlblLor (see SecLlon 2)
zlnc coaLlng ln lron or sLeel confers caLhodlc proLecLlon (see SecLlon 3)
7 CC88CSlCn8C1LC1lCn/8M
(b) Alloyloq tbe metol Lo produce a more corroslon reslsLanL alloy eg
sLalnless sLeel ln
whlch ordlnary sLeel ls alloyed wlLh chromlum and nlckel SLalnless sLeel
ls proLecLed by an
lnvlslbly Lhln naLurally formed fllm of chromlum sesquloxlde Cr2C3



2 Cond|t|on|ng the Corros|ve Lnv|ronment
(a) emovol of Oxyqeo
8y Lhe removal of oxygen from waLer sysLems ln Lhe p range 6383
one of Lhe componenLs requlred for corroslon would be absenL
1he removal of oxygen could be achleved by Lhe use
of sLrong reduclng agenLs eg sulphlLe
owever for open evaporaLlve coollng sysLems Lhls approach Lo
corroslon prevenLlon ls noL pracLlcal slnce fresh oxygen from Lhe
aLmosphere wlll have conLlnual access
(b) cottosloo loblbltots
A corroslon lnhlblLor ls a chemlcal addlLlve whlch when added Lo a
corroslve aqueous envlronmenL reduces Lhe raLe of meLal wasLage lL
can funcLlon ln one of Lhe followlng ways
(l) anodlc lnhlblLors as Lhe name lmplles an anodlc lnhlblLor lnLerferes
wlLh Lhe anodlc process
le le++ + 2e (1)
lf an anodlc lnhlblLor ls noL presenL aL a concenLraLlon level sufflclenL Lo
block off all Lhe anodlc slLes locallsed aLLack such as plLLlng corroslon
can become a serlous problem due Lo Lhe oxldlslng naLure of Lhe
lnhlblLor whlch ralses Lhe meLal poLenLlal and encourages Lhe anodlc
reacLlon (equaLlon 1)
Anodlc lnhlblLors are Lhus classlfled as dangerous lnhlblLors" CLher
examples of anodlc lnhlblLors lnclude orLhophosphaLe nlLrlLe
ferrlcyanlde and slllcaLes
(ll) caLhodlc lnhlblLors Lhe ma[or caLhodlc reacLlon ln coollng sysLems
ls Lhe reducLlon of oxygen
ZC2 + 2C + 2e 2C (2)b

8 CC88CSlCn8C1LC1lCn/8M
1here are oLher caLhodlc reacLlons and addlLlves LhaL suppress Lhese
reacLlons called caLhodlc lnhlblLors
1hey funcLlon by reduclng Lhe avallable area for Lhe caLhodlc reacLlon
1hls ls ofLen achleved by preclplLaLlng an lnsoluble specles onLo Lhe
caLhodlc slLes
Zlnc lons are used as caLhodlc lnhlblLors because of Lhe
preclplLaLlon of Zn(C)2 aL caLhodlc slLes as a consequence of Lhe
locallsed hlgh p (See reacLlon 2(b))
CaLhodlc lnhlblLors are classed as safe because Lhey do noL cause
locallsed corroslon
(lll) adsorpLlon Lype corroslon lnhlblLors many organlc lnhlblLors work
by an adsorpLlon mechanlsm 1he resulLanL fllm of chemlsorbed
lnhlblLor ls Lhen responslble for proLecLlon elLher by physlcally blocklng
Lhe surface from Lhe corroslon envlronmenL or by reLardlng Lhe
elecLrochemlcal processes
1he maln funcLlonal groups capable of formlng chemlsorbed bonds
wlLh meLal surfaces are amlno (n2) carboxyl (CCC) and
phosphonaLe (C32) alLhough oLher funcLlonal groups or aLoms can
form coordlnaLe bonds wlLh meLal surfaces
(lv) mlxed lnhlblLors because of Lhe danger of plLLlng when uslng
anodlc lnhlblLors alone lL became common pracLlce Lo lncorporaLe a
caLhodlc lnhlblLor lnLo formulaLed performance was obLalned by a
comblnaLlon of lnhlblLors Lhan from Lhe sum of Lhe lndlvldual
performances 1hls observaLlon ls generally referred
Lo a 'synerglsm' and demonsLraLes Lhe synerglsLlc acLlon whlch exlsLs
beLween zlnc and chromaLe lons

3 L|ectrochem|ca| Contro|
Slnce corroslon ls an elecLrochemlcal process lLs progress may be
sLudled by measurlng Lhe changes whlch occur ln meLal poLenLlal wlLh
Llme or wlLh applled elecLrlcal currenLs
Conversely Lhe raLe of corroslon reacLlons may be conLrolled by
passlng anodlc or caLhodlc currenLs lnLo Lhe meLal lf for example
elecLrons are passed lnLo Lhe meLal and reach Lhe meLal/elecLrolyLe
lnLerface (a caLhodlc currenL) Lhe anodlc reacLlon wlll be sLlfled whlle
Lhe
caLhodlc reacLlon raLe lncreases
1hls process ls called caLhodlc proLecLlon and can only be applled lf
Lhere ls a sulLable conducLlng medlum such as earLh or waLer Lhrough
whlch a
9 CC88CSlCn8C1LC1lCn/8M
currenL can flow Lo Lhe meLal Lo be proLecLed ln mosL solls or naLural
waLers corroslon of sLeel ls prevenLed lf Lhe poLenLlal of Lhe meLal
surface ls lowered by 300 or 400 mv
CaLhodlc proLecLlon may be achleved by uslng a C power supply
(lmpressed currenL) or by obLalnlng elecLrons from Lhe anodlc
dlssoluLlon of a meLal low ln Lhe galvanlc serles such as alumlnlum
zlnc or magneslum (sacrlflclal anodes) Slmllar proLecLlon ls obLalned
when sLeel ls coaLed wlLh a layer of zlnc Lven aL scraLches or cuL edges
where some bare meLal ls exposed Lhe zlnc ls able Lo pass proLecLlve
currenL Lhrough Lhe Lhln layer of surface molsLure
ln cerLaln chemlcal envlronmenLs lL ls someLlmes posslble Lo achleve
anodlc proLecLlon
passlng a currenL whlch Lakes elecLrons ouL of Lhe meLal and ralses lLs
poLenLlal lnlLlally Lhls
sLlmulaLes anodlc corroslon buL ln favourable clrcumsLances Lhls wlll
be followed by Lhe
formaLlon of a proLecLlve oxldlsed passlve surface fllm

ACkNCJLDGLMLN1S
1hls maLerlal has been edlLed from Lhe orlglnal work of
v AshworLh
C ! 8ooker
CharlLon
! ! lalrhursL
8 lalkner
L !ackson