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