Cuarrer7 a rocesses, During ae (a gh EY I required. Consequently slated pure energy state) than their correspondiny id : ponding ores. ae put into Use, in various forme, they are eae (Or lower energy state), Hence when metals ios 0 he aed mt sr gy “Tel ovine cha dry gues, masse Bee eceiann ie, conversion into more stable metal com: eeerondinnls ohare iy comet contact ‘with gaseous and/or liquid environment sco metalc cesta re tition or dteronon f ema srs te sufece Tis Mitt Ge, smart racic a nee ema ell teensirnent reece E pee eenen (or destruction) and consequent loss ofa solid metallic meterial, through seal comealon, Tha nal chemical o electrochemical attack by its environment, starting at its surface, o Pee hus, corrosion is a process “reverse of extraction of metals” ‘meee niliar example of corrosion is Tusting of iron, when exposed to the atmospheric conditions. During this, a layer of redaish scale and powder of oxide (Fe,0, ve formed, an the ton becomes weak. Another common example is formation of green film of basic carbonate [CuCO, + CUOHDa] on the surface of copper, when exposed to moist-air containing carbon dioxide Gravity of corrosion problem : The process of corrosion is slow and occurs only at sufices of metals, but the losses incurred, due to corrosion, are enormous waste/dsruction of machines, exuipment ad different types of metallic products. Losses occurring, due to corrosion, cannot be measured in terms of the «ost of metals alone, but the high cost of fabrication into equipment /machine tool/structures should also be considered. The severity of the problem may be made clear by the approximate estimate of loss of metal ue to corrosion, as 2 to 255 billion dollars per annum all-over the world. Obviously, the engineer must understand the mechanism of corrosion, if its effect are to be minimized. Moreover, he will then be beter able \oaovid severely corrosion conditions and provide simultaneously protection against corrosion, 2 DRY OR CHEMICAL CORROSION ‘This type of corrosion occurs mainly through the direct chemical action of environment /atmo- spheric gases such as oxygen, halogen, hydrogen sulphide, sulphur dioxide, nitrogen or anhydrous inorgasic liquid with metal surfaces in immediate proximity. There are three main types of chemical corrosion 1, Oxidation corrosion is brought about by the direct action of oxygen at low or high temperatures on metais, usually, in the absence of moisture. At ordinary temperatures, metals, in general, are very (25) to combin— 330 ENGINEERING Chey, CHEM slightly attacke areeven rapidly ogee ala metals (Li, Ne K, Rb, te) and alatine orig (Be.Cs,5 ‘and Rance wns ih ogee ca nC ‘The reacti x tions inthe oxidation corrosion are 2M— am" +2ne Netw (Coss of ey $O,n tel 4p oF “eerony Cl (Gain of lc 2M+20.— 2M 4 not — Maaions ” Onide ions Metal oxde the sale tothe underlying mesh, bot ot & mela Both raster occur (e Fig)bu the sue rite il PO pid an the var ah of oxygen oe eet ‘appreciably smaller than the oxygen iom and conseqvently ot ech higher mobility. ma Hogar 0 Padicton) ital onde al ea ret acton utara aitsan yng NS HFN ‘mealies voip sae i Fig 4. Oxidation mechanism of metas "Nature ofthe oxide formed plays an important part in oxidation corrsion process Metal + Oxygen——> Metal oxide (corrosion product) When oxidation starts, athin layer’ of oxide is formed on the metal surface and the nature ofthis fim decides the further action. Ifthe film is () Stable : A stable layers fine grained in structure and can get adhered tightly tothe parent meta Surace: Hence, such a layer can be of inperoious nature (ie, which cut-off penetration of atackang oxygen fo the underlying metal) Such a flm behaves as protective coating in nature, thereby shielding the meal surface, The Oxide fms on Al Sn, Pb, Cu, P, ele. ar stable, tightly -adhering and imperoous in nature, Consequently, further oxidation corrosion is prevented 10* cm) ; and it is called se, when its ‘A layer scaled fi, wen it Wickes less than about 300 A(t A thickness exceeds this valuecoRROSION AND ITS CONTROL li) Unstable te, the ox 2) + the oxide layer formed, decompose a ack into the Metal oxide — etal and oxygen Consequently, oxidation corres, peels ion is not possible pean such case Thus, A. Au and Pde nt under ion corosion. epesed sytace etx LTD ae Ly +0. swencien GHD (ean Y MEN Y) vena VY Y Lill lg. 3. Vola cae ayer. (i) Porous, i, having pores or crack. In 3 ee eee eee Sa ee ‘ese race METAL Fig. 4 Porous oxide yer Pilling-Bedworth ule: According tit “en oideis protective or nor pros, fhe stun ef he ois atleast na gists De alume of th mel from rich ts formed.Onthe ther band, f the vlone of the oie Tee eri eon of ta the oxide ae is porous or now-contnuos)and hee non-potetog, bse aoe aen pe aso oggen Uhh mail ure ena.” Ts.alkal and abalinecarth mea (ike Te Re Ma) tom rie fst than the vlae of tls Consequenl,te onde ayer aces Ses aaa esetr developing eels and pores nt suture. Porm oie sl permis fc aes of en rendering metal surface (hvough cracks and pores) for fesh ation and thu, eosin cnet rorstap. vs the other hand, metals like Al forms oie hse volume i grr than the ate of etl (A) eg nay gy atherig rn poe nerfed Du oe abtenc ype oaks inthe olde fil, the rte of oxidation reply decrees 12 Be coats y oti gases ti SONCO, Ch HS, Fy fe. The cet SL STOO a depends manly om the hemi ity een teeta andthe on nls degree of attack Snes mete formation of proetive oF narprotective lis on the metal suasa SFOEENG Cte 1 him formed is protective or von porous (eg AgCL fm, resulting from the aac Partha atl sl ot extent of atack ess bchse he normed Pree fy further attack, ‘a yo Foren. Monae or oa th ufc ofthe whole met apg ieee For esample dry Cl gas etc on ti (Sn) forming ole See vo Iya Rg ry en fet meta reform nee a ID: HS at high temperature attacks ste forming a FeS seals whee pene irri normal operations, “sr tyme comoion is deo chemi ain of owing i ta gn atures on sid mca rey Succ a 2c fing a for nuclear pomee pene aren eTates either: ()dislution ofa solid metal bya laud ag Winer Sra he hid metal to the ol metal Ba thse mana a eg of the solid metal. ga % WET OR ELECTROCHEMICAL CORROSION’ comeaietl i destroyed by either dsoeing or assuming combined state ach oxide, ec) Hence ‘corrosion always occurs at anodic areas. y At anode : M — M™ tne - (ote) any Ce M™_—— Dissolves in solution, (eo FE er PE hon serceen ttt med, (i) corrason of enc arene only, ard fe) fora of corrosion praduct somerher Detween anodic and cathodic arene 4 MECHANISM OF WET OR ELECTROCHEMICAL. CORROSION At anoie area : M—S M+ ne (Qrietion) EVANS) Ue Maan a, felons REI CBE), Bh Scent. He ha een dec in te Biographical Memoirs of fellows ofthe Royal Society asthe “Far ey ofthe modem science ofconosion, and preteconotmeuls Hea Contnbatonto he abt ivaredon placing afm futon cere rent eeegar0810% AND ITS CONTROL = {On the other hand, the cathodic reve hodic rection consumes electrons wath either by (a) sealution of peste © srton oa renting on eat he s coro snirnent appl ike fee amen eruion acu mal, in adi emvroment, Conse 15 ferrous ions with the eration of = Fee ane . These electrons flow through th ai ata non) ave timiatd as hydrogen he met om anode wo ethde, where Hon ce ‘ 2H2e ont : ‘atucion | Theoverllrenction i: Fey?" Feb we Fig 5 eonani wot coos iifmyaogen evn “Thus, this type of corrosion causes “dspace of hyegen ins from the acide sltion Of lion Consent ll mets above hydrogen nh cles ses Ive ender 10 $1 nai slution wth simultaneous evolulion of hydrogen. aan be plated here hat inbydroge evouortype ocr, the anodes ae usualy yt reas te cade are sal ar "ty abeorption of oxygen: Rusting of ion in natal equconssluton of cis One ien oa femesperc nggn sa conmon expe of hk pe of aT I cated wth at tin filo ion oie, However, this wom oxide fm Fg, 6. Mechaniam of wal arson by ‘one| ENGINEERING Chee ‘he metal forms large cathodes ‘At the anodic areas ofthe meal ion) dissolves os ferrous ions with liberation Of electrns, Fe re 26 (On ro are neg tOne lows rom anodic o ethic ares, through ion mat ‘lectrons are intercepted by the dissolved oxygen as i 30,+H,0+2e —20H- tat The Fe ions (at anode) and OH" ions (at cathode) diffuse and when they meet, hydroxide is precipitated, Fe*+20H-—— Fe(OH), | (© enough oxygen is present, ferrous hydroxide is easily oxidised to ferric hydroxide 4 Fe(OH), + 0,421,0 — 4 Fe(OH, ‘This product, called yellow rust, actually corresponds to FeO. HO. 112 ¥ the supply of oxygen is limited, the corrosion product may be even black anhydrous ‘magnetite, Fe,Oy. Note} Hay be pied out that hough het ects Fe?” and OH oii fom he sine onan eta th combination cer more commen nea heated terse ae 5 GALVANIC (OR BIMETALLIC) CORROSION When to dissimilar metals (eg, zine and copper) are electrically connected and exposed tom sletrolyte, the metal higher in electrochemical series undergoes corrosion. This typeof orca kd {galvanic corrosion’ In the above example, zinc (higher in lectrochemica eis) orm thane and attacked and gets dissolved; wherens copper (lower in electrochemical seis or more nb ts cathode,JON AND ITS CONTROL a8 fem: Inacidic solution, the the corrosion occurs bythe hydrogen evolution process; while aor sigh elaine solution oxygen met snc "vse" absorption cccirs, The electron-curtent flows from the she cathodic metal, copper. Thus, it is evident that the cor sap rte rom etc the coresion occurs a the anodic metal; while ‘amples: () Stel screws ina brass marine hardware; o gaa ses propeller shaft in bronze bearing; Sta pipe c A) Leek tn ee Se copper wire § CONCENTRATION CELL CORROSION = ‘Thistpeofcorrosion is du to electrochemical tack on he meta sur " a onthe etl surface exposed oan lectrotyte res cir sep coti, Ty Se al eres gai om \perature differences or juat ion of slow ‘afusion of meta-ions, produced by corrosion. = ae Differential aeration corrosion (the most common type of concentration ell coraion) “xc then om prt of as exposed to a differnt air concentration from the other part, This eases ‘SS ferece in potential between differently aerated areas thas been found experimentally that ted parts are anodic”. Consequently, a differential eration of metal causes a flow of current, called the differential current. 7 Dtfrential aeration accounts fo the corrosion of metals, partly fees in a selaton, jst eles te waterine. Thus, if metal (say Zn) is partially immered in a ciute solution of neural eefeap NaCl and the solution isnot agitated properly, then the parts bone and clsely adjacent 0 BG In are more strongly aeaed (because of the easy acess of oxygen) and hence, Beane J ptic.On the other hand parts immersed to greater depth (which have less acess of oxygen ham aaasrosygenconcentrationand ts became anodic (se Fig 8).S,adifeenc of potential is created aareh cause a flow of current between the two differenally-aerated areas ofthe same meal-Zine Thtgisove atthe anodic areas, and oxygen wil take up electrons at the cathodic areas form “rydroxyl ions. Zn——+ Zn +26 (Oxidation) 40,4140 +2" 20H" (eduction) - “The circuits completed by migration of ons, through the lecteyte, an flow of econ “trough the metal, fom ane toch = a ig. 8. Mechanism of crea arain ack cued arta mmerson oa mea336 ENONEERING Charny Tansey on wr apa rn Arno yg wari ove eacpal enera t on conte) Hog N,0 + 22% rr * Mecranlam of iret aetan atch cased by he presence hops of sso on he von si "Mal disolves at he les grated anol ress whstensSoroson pci 7 (ron nyo deposton at he cao areas From the above, itis clear that oxygen concentration cell increases corrosion, but tocar hee the oxygen concentration is lower ‘70 as fc for corrosion eee Fig, 10 (a) and (0) 1-10 roe concern coain Anode ome at naccesuble este, wht oxygen ess avalable, Te cathode fms, where onjgan le heel eons, {09 Coroson i accelerated under accumulation of it sand, scale or other, contamination. Tis ie because accumulation of rust or scale or sand, ee restricts the exec of oxygen and establishes anAND ITS CONTROL. = sor ined th he tine bre around nr dh he te xvi pe ae . reby making Incest hat prt mor eet ee Pi een higher ST sean tmx ch rt ney a he ae pe eS ct to efi a of mt Fe ita ngs amen Freer ita on re-exposure to oxsing conditions pen ae_FAI=+Cr=> Be Moss ne cr ate poses tony ose in ST ste fen ee et ten Undare rapidly corroded a al nT ic omnes re que god restate ann a Slt Papo ait tow low estan inane — i in ae a fin ern sifting he antic rention and mat te PT "Ths is particulary remarkable in AL which: Fe cy tay ncn (Cm the otherhand, dilute ee cen ob aa NO) = cst nc prem fem comme NO> igh coroson seein HNO ston oer wie rong of ORR PITTING CORROSION Pilling corrosion ‘a ocalized accelerated attack, resulting the formation of crits arcund which seine niely unattached, Thus, PANE Come seri in the formation of pinks, pits and ‘oe meta, Patng sual he I erie Breakdown or cracking of the protect et Fe tn apecific posts. This gives Fee 1 Me ersrion of sm anodic ana lege cathodic ares.338 ENGINEERING Cheyer Inthe correct environment, this produces corrosion current. Breakcown ofthe protective be caused by: (sac roughness or nomnfonfsh, ()sertehes or Gt edges fing of metal df nono sens (i) aleating stress () sling na (©) impingement attack (caused by the turbulent flow of a solution over a metal sursey (oi) chemical attack ve Metals owing thei corrosion resistance to their passive state, show a marked pitin ‘ll conor wae loadl ottie@lare cuban iheltvase iver Oeeeioue TEE seal aluminium show characteristic pitting in chloride solution, The psec of he eta impurities ike sad di le, ) embed 0 he sus metal olen toting. Owing othe differential amount of oxygen in conta with these Fig. 12) the smal part (underneath the impurity) Become the aadicares and the surroundigg Parts Decome the choc aens.Intnse corrosion, therefore, stat just undemesth the mpeg Oncea smal pit forme, the rat of corason wl be Incense Fe" + 20n F(om Sencsan poses Fig. 12 Piting carosion ‘sutaco tron 9 _ INTERGRANULAR CORROSION This type of corrosion occurs along, grain boundaries and only where the material, especialy Sensitive to corrosive attack exists, and corrosive lind possesses a selective character of atacking only at the grain boundaries, bu leving the grain interiors untouched or only slighty attacked. This typeof corrosion is due to the fact that the grain boundaries contain material, which shows electrode potential more anodic than that of the grain centre inthe particular corroding medi, This may be due to precipitation of certain compounds at the grain boundaries, thereby leaving the solid metal solution (ust adjacent to the grain boundary) impoverished (or depleted) in one constitient. The improverished solid solution is anodic with respect to the grain centres as well as to the precipated ‘compound, so that it willbe attacked preferentially by the corrosive environment (se Fig, 13) The grain boundary type of corrosion is, generally, encountered in alloys. For example, during the welding of stainless steel (an alloy of Fe, C and Cr), chromium carbide is precipitated at the grain boundaries, protected gra ‘cae ead) morowsea an tendary (08) sg FI-18.Goneral errand ackgonn0Si0n AND ITS CONTROL sey, region just adjacent to grain bou a oc with respect 10 th Pilar a he soi keel it dept in chromium composition and is ‘ol ce ason, it is also anodic to se eet the ral “fame reas is to the particles of the hel COC cher in rom ously corrosion in welded Homi carbide uly Je sans te absence raat shrement en, po) ss ion, ee coroner ng welding. Howevey whe sine doar em ie Be seroma aan chrom by rier ae te [erat 005%) Ho ord, but genrly the common DAC cae ni Fee epee men OO cree lta by he ation Intergranular corrosion olows th path of grain b giout any oparent external signs of ny neice ahct Cane a e ines aac On ace eat-treatment flowed by rapid quenching Yo aout teh raster Sere heterogncous precilatin that, ual 40 WATERLINE CORROSION When water is stored in a ste tank, is gem ferrets lc elo aie al bath ind eee sees teigh Teos sare Se wteine(highly-oxygenated ana th exh ant comply aed yc However he wateris ell fe hom acy leconein aes ace i), For the gy agentes ‘Shouse ho=w soKr mp ¢ CER eeieenOn heresy r) The problem of waterline corrosion is alto that concems maine engineer. In the case of P engine: auips tt Bt comcion sen scleral by marine plants atchingemstes tothe es Bee Tne use of apc niling pits sri ts fo some extent 41 STRESS CORROSION Renae cain for srs cracking is he combine fit of static ale dries andthe Sore a Minchrocteedy highland atckccuring when overall Her sens orn our (pre of tte ses 4 0) 2 7 Gaoson neil. Fors econ agers ave highy specicand slave seh a a vlan er et) ec of amr for ba Chord solution for sae te is Ta nascent oie of rn los he Nhe ae ne TRS tere er cased by en weg Hh ang, devi Bell Drs cr pe aie rn a ne ar cre cro cing mere al Bee i ge irre te ee eee fr rt dso ah ete iT Daan ©Res ENGINEERING CHEMSTay chemically-active that they are | formation ofa crack which stress), anti fibure occurs attacked, even by a mild corrosive environment, resulting in the ‘grows and propagates in a plant (perpendicular to the operating tensile fr it may stop, after progressing a finite distance. Fig. 15. Sess conesion, Some typical examples of stress corrosion are given below : (2) Season eracking iv aterm appli to tres corrosion of cope alloys, mainly bases. Pare coppers |mmuneto ses corosion but presence of small amos of alloying element (ike AS Se, Za ALS) elt inmarked sensitivity. For ecamples alpha brass which when highly stressed) undergo intergranlat cracking in an atmoephere, containing traces of ammonia or amines, Theattck eure lon the rin boundar, ch !ecume nore ano th espe othe gan heels (probably duet disorder of atoms, caused by diferent ‘vientation of adjacent grat). Both Cu and Zn ae electrochemical very active in ammonia solitons (Sue othe formation of stable complex fon Cu(NE)}* and. Zn(NH9* respectively) This is the rel cause of Aissolution of bras, nitating in ssure which ultimately propagete, resulting in the formation of rack in the presence of high trl stress (0) Canatic ambiitlaoent i very danger frm of eran corcion, curing in mil tel expe tein salto thigh tempers and ass Te alae often tsceted wit team bolls and Rsk transfer equipments which water of high tality tacks the mld sel plate, particulary atthe crevices "ear iets. Bolr-water, sally, contains a certain proportion of sade carbonate added for wate sotening Purposes. In high-pressure boilers, hs breaks upto ge sal lyri and carbon dx, 'NosCO}-+H,0-——»2NsOH + CO, T and makes boiler-water elaine. Ths very dilute alkaline boller-water (in boilet) ows into the minute haircrachs and crevices (oy capillary action), where water evaporates and the caustic soda corcetraton buds up. This concentrated alkali dnsolves iron a sodium feroate (hypofersit) in crevice, cock, whee {he metal is stressed and the concentration of alate mach higher than that in the body ofthe liquid. The sodium ferrote(NegFen decomposes a short distance away fom ls point of formation according to eiher ofthe following reactions : 3Na.FeOQ) +4 HO ——+ 6 NaOH + FesO, +H or 6NagbsO,-+611,0 + 0; — 12 NaOH +2Fex0, Sodtum hydro sregeerted and magnetic (te\0) i rected, Hereby enhancing further dissolution fiom ‘Caustic embrittlement can be explained by considering the following electrochemical cll: “Iron | Concentrated NaOH | Dilute NaOH | fron ‘The iron surrounded by the dilute NAOH (main body) isthe cathodic side ; while the irom in contact with rather concentrated caustic toda (eq,crevices, haincracks, rivets) isthe anode portion, undergoing Corrosion and is thas dissolved Prevention of caustic embrittlement: The best ation of edi sulphate fo the oiler ter. Another {stousetonnt olga dive othe oler-water, Both these methods revert cause cracking by blocking Up the haircracks and crevices with innocuous harmless substances, thereby preventing the sodium hydroxide from infiltrating,contin AND TS CONTROL GALVANIC SERIES n the electrochemical series y,a metal high in the series fected. tere alloys. Consequently, a more Sarby Ait eae Fis, galoanic series give real and useful i it For example, Li corrodesf that metals like Ti and Al devel imng their effective electrode potential From the above, itis clear that le an (reduction elect trode potential ‘more ano PL arranged down nan increasing faster tan Mn dre coroner ian ich coro faster than fe Fe corres fer ever, sme exceptions tots groin ial ere) sen seat then Ai Th cored while Alcs caved eel Patt 0 ht predate by enlace sgt enel adhering oidelnymen taeeinces ey mor positive a sn ngan) troche series desma Practical series, eted ga ‘of melas and aay infomation stone Table. Gans a given environment like seawater ‘he corrosion of metals ad alloys, Se aT a Megalloys 2n Al ca Alalloys Mild steel Cast iron igh Ni cation PhSa solder Pb Sn leone Ni-Mo Brastes UeNi20=Curat=Fe) Silver solder cu Ni Crstainless ste! 18- stainless steel 18-8 Mo stainless steel AB. T Graphite Au Pe [ee cate eal alloys“ ENGINEERING CHEaGr py 13 FACTORS INFLUENCING CORROSION The rate and extent of corrosion, depends on the following factors A. Nature of the metal: () Position in galvanic series: When two metals or alloys are in ‘contact in presence ofan electrolyte, the moe ete metal (or higher up inthe series suifers corso, Thy and severity f corrosion, depends upon the difrence in tir positions, an gener the ference, the fay {he corosion ofthe anode metalloy me {3 Overvatage: When a metal, which occupies a high position in galvanis {in IN -H3$0,, undergoes corrosion forming a film and evolving hydrogen g8, the initia ae of egy is quite slow, because of high overvoltage («0.70 V) of zine meal, which reduce the efective elergy Potential ta smal valve. However, if few drops of copper sulphate (CuSO) are added the coroson a Of zine is acelerated, because some copper gets deposited onthe zi meta, fOrmng MMW ches, whee the hydrogen overvoltage is only 033 V. Ths rection noveratag ofthe coroding melllly acer corns ie Relative areas of the anodic and eathodic pati : When two dissimilar metals or alos rey contact he corrosion of the anodic prt diely proportional othe eat of aren of he cathodic arta nadie pert a Corrosion more rapid ant secre, and highly cle ifthe anotie are is small. 0 sale ‘fit na large copper tank) becmse the current density a «smaller anodic aren muck 7, end he dena ‘lectrons (oy te ng cathodic areas con b mel by sailer antic ares oly by undergoing oon moe ily (Go) Purity of metal: Impurities in a meal, generally, cause “heterogeneity and form minting clectochemical ells (atthe exposed parts), and the anodic parts get corroded. For example, zine meta Containing impurity (such as Po o Fe) undergoes corosio of in, duet the formation of local elerchene Seal celle The rate and extent of corrosion increases ith Ue increasing exposure and sten! of the impute {Consretly, corrosion resist of metal may be improved ny resins Pury “able 2 Flecrocheml series ess glances, Electrochemical sri 1 Electrode potentials aremeasured by dipping pure “This series was developed by studying cooion melas in their salt solution of IM concentration, towhout any oxide film on them. ‘The position of a gives metal in electro-chemical series is fixed It gives no information regarding positions of alloys, 44, The position ofa metal in this series is ‘Teapot permanently ‘This series comprises of metals and nor-metals. It predicts the relative displacement tendencies. ‘of metals and alloys in unpoluted seonate toot tir oxide nef my enor ‘The position of giver metal may shift in gala ‘Since alloys are included in galvanic sere, s9 thei corrosion cam be studied from this series, “The position ofa metal, when present inthe frm Bra alloy ls eferent rom tht of pare metal “This series comprises of metals an alloys. Itpredicts the relative corrosion tenes (0) Physical state of metal : The rate of corrosion is influenced by physical state ofthe metal (sch 5 grain size orientation of crystal, stress, et). The aller the grein-sizeof the metal ov alloy th gre al es Elbit and henee, veer wl Be is coreson. Moreoer ares oder tres, een i pre meal, tnd beams and corrosion takes place at these areas. (ci) Nature of surface film :In erated atmosphere, practically all metals get covered with athin surfs film (thickness =a few Angstroms) of metal oxide. The rai ofthe volumes ofthe metal oxide 0 he meal st cee ereeiic volume ratto” Greater the specific volume ftio, lesser is the oxidation corrosion ra. The Spctite volume ratios of Ni, Cr, and W are 16,200 and 36 respectively, Consequently, the rat of ovation of tungsten is least, even at elevated temperaturessen0sion AND TS CONTROL viyeassive character of metal Met = Ferree eh ere npn fon) on herman ae Se eet alee mannan poe a ea x reps eon eh Ai eva fae pvaating characte ferent ing ios Th Sen ere tagasel solubility of coroion produc: decry mente coe prc electrochemical crrosion, fhe corrosion pode sole in faster rat, On seer se aoe os nthe contrary ifthe erosion pric nol tt ther insoluble product (eg., PLSO, formation in cose of Pb eee ees Sint cermin p hr ne pei aa (Lean er inna roe aah ee oor oe carpe yf aby eon oe eye ite wn) Nature of the corroding vironment Temperature : With increns of temperature of enironment, the reaction a sl os dso rl er @ awry errno oe gverally enhance eeu of i he ering ft ampere eines eh ‘edt namin rte ey eee he pel rls of tml wi ery esata sn tl becomes term mi ope ed cee eee Ca pa ong tues menu rot ie colina penn rn i ny ymin tt im fis ered ont a me ere ofeach) NPE Tomson cos pe Srosonesnr Fen ee info Pepe es tow : ee ee nrpesTiensa an enced aoxp= sock ay pe oe Hons eceponl are eC eas sente aa cm of muses In stonger: Aone, nie ey a Oy ern ts ke CO> He, SO and fries of HHS, 0 Se ne gs he yo Sr tel een end i rial ed a onaeguenty als Fn ret Hoang he al cme ae na ‘coe So re es EN en a ire Sy orn wt mre ery EEN PS a i ogden mene TN en ietbe aA cy ae mei NES Sees er per ingen Ee ne “peat nace tens hr ge a ne En Per scowl i Me cn riancand ne ed Fea ie barca at sain comin te Sor oe tl at cen een cee acm gry oon me eal sy mccang ep kr Ce mpl ome me) ee ch nce 268) See ama coreion at pH 1 one: remade redo he oan of insoluble ee ect an i ag ones presen an re en ae ef, eco s etiy srtace fr sh nd ing en sng te Tg medium cota #0 oma Mn eee yen er me EEE(a) Conductance of the corroding medium : In corrosion of underground ot submerged {eg conductance ofthe medium is of prise importance, Conducens of Gt eomteeieee lower than torte asrinrad seis Consequently, amy erent (rom power leskages) wl ca ‘ote metlic structs, buried under clayey and mineralized sols than tose under sands ia? Formation of oxygen concentration cll: With he crete in supp oforygenes theme Ele te corrosion is promote. Less exygen concentration (eg.onidecoated par or ls spond pa ding toe mere-onygenated regions or pars more expose t oxygen) Cees? ata “Revsby lading tothe formation of “oxyge-concrtation clin thick the med pa eee coroion 8 At the cathode surface, electrons are consumed, This 2120+ 0,4 4¢-_ s0n- (Catt rt Supply of electrons (for oxidation) take place on the anodic parts, Thus Fe Fe 426~ (Anat acing ag enation concentration ell promotes corrosion but occurs where the oxygen ‘oncention tue) atelin corrosion of buried pipelines and eables, passing from one type af coh another and ‘erosion are due to the formation differential oxygen concentration cell oe {) Flow velocity of process stream : Flow velocity plays an important role ina corrosion, hich sa ulisatayron, suction progresses, the potential diffrence between the enedic aq ‘cathodic areas sree imately steady state, called corrosion potential Emp) wecheds ee sum ofthe rates of concen oxidation) reactions become equa! othe sum ofthe rats ofalcatnecs (reduction) reactions. The Othe caer eae aunt a hs pote is called arronn caren (heh vee ate depends on tap reartent densities atthe anode and cathode, i) potential diffrence bern, the anode and the cathode, Ceentve areas ofthe anode and cathode, () polation chatacters well as cathode and! (©) temperature ‘ean Anodic current density (1.)~ Cathodic current density (1) {0 Ui the cathode areaislyger than the anode area, then the anodic curent, tensity, (current flowing to wl ba ae ten node) is reter than the athe curent density, 1, Evident ence oe (10 wil be larger and hence, the anode material undergoes accelerated onnoonenon HTS CONTROL ms preg ten plaaton et JT 6 he corosion ay either anode or cat wo = thode or both, the mrs the corrosion mon ie oe cme re res en rn Sra Pe te et canna ae Se aaite rac sana ta re Brrpremistarua teeta saa ie 10. tates ert cuisines tere pntntaa) Tews ve Me typs fp “July nde nine area sen tert ee. rosioncusent and corsion rate is controled PY spy tt mainly end undergoes polarization the, eae petmaton erg 160) comosion current and coresion rates controlled PY st teth the electrodes get polrized, the conoson caren spb gsnm sone mibel or B10 rent and coos rate canted by bt 2 ne + } a i i is a (meee omer > Spa Smee a mass sro 18, Ear ition game: (ae (cae eon emonve nvrcnment oer coronene ASSES OE node Fon whether ty ea Note Iniilors ada er caidas enteral _gcions or bh Consequent ‘Goccoreatodic reactions 44 CORROSION CONTROL (PROTECTION AGAINST CORROSION) some ofthe corrosion conta method ae described as follows qLpvoper designing : The design of te melee heal be suc that “corrosion eve if OEMS Asuniform a ds not rest nites a ey coon’ portant design PINES oe of corroding soaton this pNP, dissimilar metals in the ESE te Pe active metal (i the imenedine CY of (Aco the contact of. ot flwed tne corrnon oh Guta) he ea ative mets Toma protected hen ro sar mse 0 ne she anodic material should have 08 Tse ee ee ck meter aren a poss mate ed, they showld be as lose as owes 12 in tn disinar metal incom ‘each other in the electrochemic 27%, Hoy Whence he arc ji of PT stay wei, an aang tng Ma ir etiam pled in-between them fo 00 metal-melENOMEERING Coat (Pn anodic metal should not be painted or coated, whe in contact i dingy ‘abi metal because any breakin conting would lead to rapid lod oor y tier tevent the occurence of inhomosentites, both the metal and inne, cores en rent Thus a proper design should mod teoreen ape mo Cio thc of te sme ely sne eee ee et Bole tr. therfore, nese for ths reson athe ye (ee Bg. 17) When its imps med oes ona mind, he carding men dena esa stent ———— BS =e eatin because they easton, ee.) of the equipment. Sharp comers and reece, shonin ‘ded, because they favour the formation of stagnant areas and accumulation oh te: (se Fig. 18), lg. 19. Provetion of conceon by design.“GORROSION AND ITS.CONTROL ow {i Uniform fw of corosion igi ile ff corn is dil, ce bt sara aren nd get Beppe be ecules much spray nan aN nnn condi a —_&) A proper design should prevent condit | BShinienis oa Mm subjecting some areas of structure to stress (cold li Sel Gee Fig, 19), IP galvanic couple with a non-stressed (not worked) areas Peis pore meta: tris meel o t 2: ig ore metal nti am mehr hh eres cron ile of Bas ra Coane ene ane er cenarae Puraton of metals ct, Provides led npn oa io hl ut, when vpn ithe corrusion resistance of. we of « purified metat depends om the mature uf worreaive environment Fer nc of Al depend on sone fim formation, which a highly protective oy SRinthigh pty metal Hoseever, nothing “ y Ba age es erat arg at al ee Bao ccs tpn tax melo nh eeprom cm a oad or ny properties ete ing Th hegre pt ged er Ee rela a rene ocean areata! nat yd cem ace on Oia mca ec age Nott pcs ew pln ad ie rs ent a ns a ee ee Grrnon restanc, alloy should be completely homogeneous. Cron ihe st watable alloying 9 eee are akCaemineanyswpclcefn See ee Prose aa) awa eae res aon Te pcp eve nha mod min re te en pe Pt Fey hc dni omar Taree pp fsbo ree ficial enodc protection method: nhs protection tod he nic trac fo i ana cegnc ton woe atic metal olthcirsn s concentrate a Ihe ee a re ela tal gt crroded lly ote paren sacar ed) Fe el Cee nce met socmpoyedin cet sor ene Teoreded oe) igre The mer ae ore hen cna completely Meas commonly employe _ mde lock is rma estuarine als, mpotant oppo of 2 eric ano ade proncton of tue pipeine, underground cable marine Sater spl wotertanis, pes fe Fs 2) canes prtcon mano amare rong easing maa sae 2. a seg wpamen wane MOH rt sapien oan on elle protectin: mai 4 Rt ST a apr ce enna nee ra a tee Fe pers prenad current deivd om ae =~ “an (ike battery or rectifier on 1oes ENONEERING Creag 2 tne) with an nae mde graphite, highs ito, Srp ion tunes ste ‘Tam Unlly. sulfcent dc. current is applied to an insoluble anode, buried in the at inmeed inthe cording medium) an emer othe metal secre oe ee Ey 2 Te andes wy ns hl mpd ef che eee Pm) ee se eral etn wah urs Ths pe ef adc pron as ‘ope woerbox cs ater edo ater ppc, condones arena tore Man i nips Ths ees pny pe Srectre rng tm opto a mores er cose ttn, sectors spon 5. Modifying the environment The cormsve nature ofthe environment can be ri ther: (0 By the removal of harmful constituents, or (i) by the ation of specif substones ea, ‘mextrlie the eft of corrosive constituents ofthe irom (@) Deaeration. In oxygen concentration type of corrosion, exclusion ofaxygen from _rsirrmont recs metal coreson. Expulsion of dsolved oxygen is done by adstnonof feos ctor egster with "mecha gation” Tmo als eics te CO, cto eater oly ‘decreasing the corrosion rate of stel pipelines carrying steam condensates from boilers (® Deactivation inclces Ue addition of chemicals capable of combining opi ithe oxygen in aqueous solution. For example, sodium sulphite (NasSO). 2NaSO, + 0,+2Ns,S0, “Hydrazine hydrate (NH, . NH. H,0)is advantageous over the sodium sulphte, because the reaction products are Nz(@) and water. GH, + ON, +2H,0 (©) Detaoidification races the moisture content of iro suchen extent that he aunt of er condensed on metal i too small to cause corrsion. Alumina or eilica gels, which adsorbs moatag preferentially on their surface, are used only in closed ares like air-conditioning shop. (2 Alkaline nextralisation i> precetin of cOresion by neutralizing the aide character of corrasie excironment (due tothe prsente of HS, HCI, COs, $0 et). Such alkaline neutralizer ike NH, NaOH, lime, naphthenic soaps, etc) are, generally, injected either in vapour or liquid form to the corroding system orto its pars. This method has been widely used in conrallng he corn of refinery equipments. 6 Use of inhibitors: A corrosion inhibitor is “a substance hich wen ced in smal uamtites 40 the agucous corrosive environment, efetoely decreases the corosion ofa metal. Inhibitors a (0 Anodic inhibitors (uch as chromates, phosphates, tungstates or other ions of transition ‘elements with a high oxygen content) ae those that sife the corresion reaction, occurring atte anode, by forming « sparingly soluble compound with a newly produced metal in. They are adsorte onthe| sqosi0N AND ITS CONTROL sec se formin; a rote fn oF barr, a theres Ja control is effective, yet it may be dangers secre corrosion rate, Although this Facer eth yams nn El Sn, one {i9 Cathodi nygroBe®- inhibitors: (a) In a (@) Im acide solutions, the main cathodic reaction is evolution of 2H*(aq) +2, HA) Consequently, corrosion ma Caen orion ay be ec tery sig rr esis fed renee, imresng hore of yen nation. The dfsion oH ons ‘esd deena by re hire ie amine nape tte to wo sed wes and thous hay meal vp) whch opt sficingedcobed at txides (or salt ke sodium metraseite) ae wed 95 1 ator, bessse ey dst eden fn of enc eno etna a coarser ‘poreasing considerably the hydrogen overvoltage. a 2 (In natural solutions, the eathodic reaction is: H,0@+120,+26 —20H (a) ‘he corosion can, therefore be controlled either by clninatng oxygen rm the coding Pei by reting ts fino ota tial The rte eat eee waaay agents (ike Na;SO, ) or by deveraton, The inhibitors like Mg, Zn of Ni salts to the Thoorments reused in the ater ase. These ect wth hydrox fons (ot the cathode) Forming saver rcnginsolble hydroxides, which ae deposited on the cade forming, more oF les pmb sf bree. 7. Application of protective coatings: Protecting the surface of an object by the application coat probably the oldest ofthe common procedure or corrosion prevention. cated: seer Shae the underlying meta frm the cording ernment. Te ony sation of ts sa ihe service behaTour ofthe protective coatings: () The coating applied must e chemically ae ne vicen under parte conditon of temperture and presse (i) Moree, coatings aa he ponetraton fe noon he atrial whch ey pote. bre esrption TYewb important protective coatings i given below Dano conting are produce rom contin wih are “anit the ase metal Te eet or cramp, contin of Zn, Aland Cd on see ae anodic beau thet ae ea eer han tthe ase metal on any poe break dicntinutis See oa eesti a galvanic cells formed between the coting etal and the er a a in eof gleied sl eh coing metal ing ade) snctonin ot node aig ste, Zn sare an anode; wl on lee anes Fig. 22 Funcoing oa on peed event expoed ena ao :30 ENGINEERING CHEMigty tacked; ving the undernoted. Galvanic cli formed. tnd teenporn ace ane arate) Uoslvessnelealwheves he in ah Cathodic) protected (ce Big 22) Thus, no attack on the ron occurs unl practically all hee has ft cortodel nthe wc ofthe expased iron spot S, rte coating protec ion saci (i) Cathodic coating are olaned by cating 4 more noble meal (having higher potenti than bce etal Thy protect the bac metal because they have high creo rey than the base meta, Cade caring proves eto protection fhe ase metal onl hen ye completely continuous an free from pores, breaks or discontinuities. or ifsuchconinge ave pctured, uch more corrosion damages canbe done fo th bse mea See eee ee the eta ofthe metal completely covered, sinc in is owe than iron in electromotive sf Howeecs cure cotng punctured, he tn becomes the ctoe ; whe the exposed on hig Pewee escent pene en Be ie om on Fig. £3. Tin-pated sel. The protect te on, when the cong s conncus ‘iho tne coatings broken the Fo othe te! becomes te anode Ged abject io acceleraoa lea oreo. localized attack at the small exposed part occurs, resulting in severe pitting and perforation of he base ‘ital, iron. Such combination of a smal anode and large cathode area is always very dangerous. Table 2. Anodic versus cathodic coatings. ‘Anodic coating Cathodic coating Tr Prout the underiying base meal srfily._| Protea the underlying base metal, ductois eb Gara and higher coro reson 2. lecrode potential of coating metal i lower than | Electrode potetil of coating metals higher than thot of the base metal. meciicteeeeny hn 3 431 prnes, breaks oF discontinuities ogcur in such 2| If pores, breaks or discontinuities occur in sucha Tobing: the bese metal sot corde, til all the| coating, the, corrosion ofthe Dase meas sede ‘coating metal is consumed. . 4. Coating of Zn on ion isan example. Coating of Sn on ron is an example “Methods of application of metal coatings : (1) Hot dipping is used for producing acting of tow-melting meta such as Zn (mp. =A19°C), Sr (mp-= 732°C), Pb, Al, et, om ion, steel and compe, cuhich have elaticely higher melting points. The process in general, consist of mmersing th ise metal ina bath of the moliencoating-meta, covered by a molten fix layer (usually zinc chloride). The fx ‘leans the base metal surface and prevents the oxidation ofthe moter coating-metal. For good uesion the base metal surface must be very clean obherase it cannot be properly wetted bythe motes ntl Te ‘most widely applied hot dipping methods are:a0 08 AND ITS CONTROL Mie mn noon een ara aes cia terial al rege pon rn ay ahh ein a ae cry te ee ei inane son ee Seta of cron produce dcchema cae te rest omc th rset a fate me On sr re a ti Dt ete ern Ree ee ‘Sysstat rin teat ncn hry appre frier ovo every enn os pr i iz 9 en Sorta rhe ok ise op nd cot pura ee ple malyodenmn ode (MeO,, the xan careHion nature of the coroding ecironnent nA {) Temperature : With increase of temperature a Sepals of tmperture of envionment the renton as ll as difsion rte incr, Baayen ang eo Diy oa moh Cre hay fr site ee nepal Senedd res tp a dt oa goe Cronos os ere oe perefurisheterto tele, seta for sting pan ee ingup an electrochemical corrosion cll Moreo¥= seer sf om ametal surface hough sold bdy, yet poses the prop ofa i" Brad cre mn yee yoo a enon creed ean a eI ete be ney mess cme Fare yao po finfon ines Tsien anna PS ack eof meceponal ae. Ci ew La fim i sierra nib i fa nT SS Sct oat cag pmo Pe Sr cman nea me ccleaner il nr Rog ee Sa ey er bepeeee nena samy Sa re the met nce ey ren NT a gpa in mere, a al te ano Pr pel OH, ce sare cig een ne rn race ang ce pir ga Te fon oxygen: free water i i pe coresponding conn at ese ae shee ce ren Beveduced by inressing the PH he tang ewe i ed, enenin wen ac scans 00h 8 abonic aid) ri ie a ements we ee be ne ln a = snr tain, tr SP cg a ‘oa a ry er on a abet Crone Many tl gp rey meen ie eit econ oe fee aren