» | Apaiitd Es re INTRODUCTION con cule and, alloys are generally used as fabrication. or suas ction materials in engineering. If the metal or alloy fa ares are not properly maintained, they deteriorate slowly a he action of atmospheric gases, moisture and other ‘emicals. This phenomenon of deterioration or destruction of metals and alloys is known as corrosion. ° Definition _ ‘Corrosion is defined as the gradual destruction or deterioration of metals or alloys by the chemical or electrochemical reaction with its environment.” | 33.2e cAijses OF CORROSION Metals ogcur in nature in two. different forms. 1. Native state. 2. Combined state. 1. Native state The metals occur in native (or) free (or) uncombined state are non-reactive with the environment. They are noble metals exist as such in the earth crust. They have very good corrosion resistance. Au, Pt, Aga2 ng Chemie 2. Combine state y Por tetgania) atqedo | “Except noble metals, all“cther metals are rexctive and ith environment ani ToMT-wMe"compounids, as their ‘oxides, sulphides, chlorides and ‘They exist in their form of stable compounds ealled oret and minerals, F e203, ZnO, PBS, CaCO; ete, 3.2.1 How and why corrosion occurs? ‘The metals are extracted from their compounds (ores), During the extraction, these ores are reduced to their metallic fates. In the pure metallic, state, te, metals are unstable as they are considered in exeited stale ie, higher energy sate, ‘Therefore, as soon as.the metals are extracted from thelr ores, the reverse process begins and form metal compounds, which axe thermodynamically stable ie. lower energy state *Gtisos) panes Beer reese AERECERETSSE) (Asan of ower oe) Fig. 3:1 Corrosion and oxidation process Hence, when metals are used in various forms, they are exposed to environment, (such as dry gases, moisture, cte.) the exposed metal surface begins to decay ie., conversion into’ more stable compound. ‘This: is the basic reason for metallic ‘The term corrosion is sometimes also applied 10 degradation of plastics, concrete, wood and materials. a Const. mag anos’ familiar examplevsfieatosion inmiing of coi De +94 Og + HAO FAO GO ee eee wen a St cats ce ESE consieness on ervecrs oF coHBHEn ie eatin of coreion gro ote as fo cy oe Racin go int 2 oe guminad eww son Se caaees ome te meal Reeoe 4, Plant gets failure due to corrosion. 5. It is necessary for over design to compensate for the corrosion. 6. Corrosion releases toxic products, health hazard, et. 7. Time is lost in making available pars. 2. The value of the goods is reduce, ETE caassinicavion on THEORIES on TYPES OF CORROSION Based on the environment, corrosion is classified into A. Dry or Chemical corrosion, and 2. Wet or Electrochemical corrosion, DRY “oR CHEMICAL CORROSION Dry corrosion is due to the attack of metal surfaces by’ the atmospheric gases such as oxygen, hydrogen sulphide, sulphur dioxide, nitrogen, etc. ‘There are 3 main types of dry corrosion. Le S,/-6 Bt Engiviébriagashomist 2 \Bxidatiott- coeroitioni¢or) ‘comatiion) by-axpgin. j 2 Wisbnia ey nydrogigts — BP son 2 Hiauidetalconsion ) Br, Omcaton cotrasibn (01) corrosion by = ss Gridation corrosion is Wodki SEE ty ine aired tack cxygen at low or high tempers etl ates fn te absence of maisture Atal meals ee Nae Rene a aikaline-asth metals (vig. Ca, Sm ee) are rapidly oxicned at Jow temperature. "At high Terpemire, ain a mas (xcept, Ag. Aw snd PD are oximcs ‘Mechanism of dry corrosion (@ © Oxidation occurs first at the surface of the metal 7 resulting in the formation of metal ions (M™*), £ Which occurs at the metal / oxide interface, M—=M**+26~ Oxygen changes to ionic form (07) due to the transfer of electron from metal, which occurs at the oxides film / environment interface 402 +22" —>0* Gil) Oxide ions reacts with the metal ion t0 form the metal-oxide ‘lm, M+ 140; —>M?" + 0% = MO (Metal-onide film). Once the metal surface is converted to a monolayer of metal-oxide, for further corrosion (oxidation) to occur, the metal ion diffuses outward through the metal-oxide barrier ‘Thus the growth of oxide film commences perpendicular to the metal surface (Fig. 3.2) Nature of oxide fim ‘The nature of oxide film formed on the metal surface plays an important role in oxidation corrosion. 1. Stable oxide layer ‘A stable oxide layer is a fine-grained in structure, and ets adsorbed tightly to the metal-sarface. Such a layer is impervious in nature and stops further oxygen attack through Aiffusion: Such a film behaves as a protective coating and no further corrosion can develop. Osides of Al, Sn, Pb, Cu, ete, are stable oxide layers. 2. Unstable oxide layer Unstable oxide layer is mainly produced on the surface of noble metals, which decomposes back into the metal and oxygen. Metal oxide <== Metalt Oxygen Onides of Pt, Ag, ete, are tinstable oxide layers.gee. 3 Votaete osm pe The, oniUe layer volatilzes 36, soon as i is formed, leaving the’ mictal surface for furthér comesion. Molybdenum oxide (MoO3) is volatile. Beamretective (or) Non-Protective oxide film. (Pitling- Bedworth rule) a © | According to Pilling-Bedworth nile, if the volume Of the oxide layer formed is Jess than the volume of the meter the oxide layer is porous and non-protective, The volume of oxides of alkali and alkaline earth metals such as Na, Mg, Ca, ete., is less than the volume of the ma) consumed. Hence the oxide layer formed ts porous anit non-protective. G2 On the other hand, if the volume”Of the oxide layer fotmed is greater than the, volume of the metal, the oxide layer is non-porous and protective. The volume of oxides of heavy metals such as Pb, Sn, te," Arcater than the volume of the metal. Hence the oxide layer formed is non-porous and protective. Pilling-Bedworth ratio The ratio of the volume of the metal oxide formed to the volume of the metal consumed is called “Pilling. Bedworth Volume of metal oxide PB ratio= “Fohume af metal consumed If the PB ratio is slightly greater than 1, the metal oxide layer will be protective and non porous, - eZ, 352 Corrosion by hydrogen. dement (at ordinary iéinperaéire) 1. Hydrogei embrittlement (at ord i ‘When meals contact to HS at ordngey teipoiar éauses evolution of atomic hydrogen, Fes Hy —>FeS 4-211 ‘This atomic hydrogen diffuses readily into the metal and collects in the voids, where it recombines to form molecular hydrogen. H+H—>n,? Collection of these hydrogen gases in dibvottetiverop very high pressure, which causes cracks and blfsien on mee? Thus, the process of formation of eraéks and blisters gn the meal surface, due to high pressure af hydrogen wea 4 called hydrogen embriement 2 Decarburisation (at higher temperature) At higher temperature atomic hydrogen is formed by the thermal dissociation of molecular hyarones Heat Hj) —>2n ish steel is exposed to this environment, the atomic hydrogen ‘adily combines with carbon of scel and produces methane ean C+4H—scn,t Collection of these gases in the voids develop very high Dressure, which eauses eracking. Thus the procest of decree MeGarben content in steel is termed as “decarburisation” of steel. 98.3 Liquid-metal corrosion This is due to the chemical action of flowing avhigh temperature. The ‘corrosion reaction iavelvesEngineering Chemisty, a AE atraae— S15 vedston)) (b) Absorption of oxygen (or) Formation of hydroxide fon type corres ‘The surface of iron is usually, costed with a thin film of iron oxide. However, if the oxide filmy grows, some crack will form and anodic areas are crested on the surface while the remaining-part acts as cathode (Fig. 3.4) When iron metal contacts with a neutral (or) slighily ‘alkaline solution of an electrolyte in presence of oxygen, OW ions. are formed. Fig. 2.4 Absorption of oxygen type corrosion At anode Iron dissolves as Fe** with the liberation of electrons Fes F2* +20" (oxidation) At cathode ‘The liberated electrons flow from anodic to cathodic part ‘through metal, where the electrons are taken un by he dissolved oxygen to form OH ions ove ai /@ conesion 03+ 20 + 26° ——>20" Fe? + 20H” ——>Fe(OH) 1. If enough Oz is présent, Fe(OFi)y is easily oxidised to Fe(OH)s, a rust (Fe,03 20). ‘4Fe(OH)_ + 02 + 2H;0 ——>4Fe(OH) ‘Table 3.1 Difference between Chemical’ and Electro chemleal Corrosion it occurs in’ presence of, moisture or electrolyte Girect]It is due to the set up of a [chemical attack of metal by|Iarge number of cathodic te environment. land anodie areas. 3 [Even a homogeneous metal | Heterogencous surface (ory surface gets corroded. |Bimetallie ‘contact is she Te occurs only ia. dry [condition.. Zit is duet the condition. | Comoston Products] Corrosion — occurs —at the} Jaccumulate in the samme[anode, while produces place, where "cerrosion| formed elsewhere, ‘5. | Chemical corrosien is Electrochemical —conrosion: self-controlied, i " is continuous process. OE in folows adsorption it follows clactrochemical Examples Examples Fonmation of mild scate on|Rusting of iron in mots iron surface, laomosphereCORROSION CONTROL =——— ficial se ba aceon rae C The rate of corrosion can be controlled by either modifying the metal or the environment. 3.8.1. Control of corrosion by modifying. the metal § 1. Material selection and design aspects 1. By selection of the metal Selection of right type of metal is the main factor for corrosion control. Thus, noble metals are used in ornaments and in surgical instruments, as they are most immune to corrosion. 2. By using pure metal . Pure ‘metals have higher corrosion resistance. Even a small amount of impurity may lead to severe corrosion. 3. By alloying Corrosion resistance of many metals can be improved by alloying. For example, stainless steel containing chromiumwe VED Tr e of ‘Poor design Good desien Fig. 3.15 Minimizing crevice corrosion Revered joints produce revi corrosion, 80 welded joints are pref CORES on Costna Gi. Hectrochemicol protection or Cathodic protection “THE paReiple-MVOIVET TH the electrochemical protection (00) cathodic protection is to force the metal 10 behave Hike ng cathode. ‘The important cathodic protections. are @ Sacrificial anodic protection Gi) Impressed current cathodic protection 1. Sacrificial anodie prétection method a oe aaa wep el a na Ac cd protecting the original metalic a is otherwise known as sacrificis eae ium, Zinc, Magnesium are used (fis sacrificial anodes. "of sacrificial anodic prothetion Aone Ot wetness for tg protection of ships and oats, Sheets of Mg or Zn sre hung around the hull of ‘the tt) Zator Mg wil act as anode compared to iron tue OE oat ts made of iro), s0 corrosion concentrates on ee re Since ey are sacificed im the process of =nving eee ae called sacrificial ances (@) Roster Fig. 3.18 Sacrificial anodic protection SecriScial anode Fig. 3.16 Sactinetat ‘snodle protection“ Ce a (© Protection of underground pipelines, cables from soil corrosion (Fig. 3 18(a), 2 (© nsertion of Mg sheets into the domestic water Cea’ 1d, Prevent the formation, ot “suai Fis. 3.18) (® Caleta metal is employed to minimize engine 2 ‘Impressed current cathodic protection method opposite. decmettOd, an impressed curent is applied in the the comedltsetion of the comrasion caront to. wei ee soroding metal is converted from anode to sadeode This can be done by ne by connecting negative teal of the battery to the metallic structure, fasted (Containing mixture of Bypsum. coke, breeze, sodium sulphate). ‘The “back i Fig: 3.19 Impressed current cathodic protection 1. Ry me Applications of impressed current protection Structures like tanks, pipelines, transmission line towers, ERdsreround water pipe lines, oll pipe lines, ships, ete, ca Protected by this method) Table 3.2 Comparison of Galvanic method (Sacrificial anode) and Impressed current Cathodic method No external power aupply|Exiemal power is necessary. must be present 2. [This “method requires) Here anodes are stable and Periodical replacement of| do not disintegrate sacrificial anode 3. [Investment is low. [investment ie more ‘4 |Soit and micrebiological|Soit and _ microbiological Jcorrosion effects are’ not|eorrosion effects are taken taken into accourt. into account. 3. [This is most cconomical| This method is well suited method especially when|for large structures and) ‘supply [shorter protection’ is|long term operations required © |This_method ie suftabie|But thie method can be when "the “current|practiced "even if. the requirement asd the|enrrent requirement and the resistivity” of thelresisuvity of | the electrolytes are relatively electrolytes are high. Tow.INTRODUCTION Protective coatings are used to protect the metals from Corrosi: ‘on. Protective-coatings act as a physical barrier between the coated metal surface and the environment. are also used for decorative purpose. Protection and decoration, such as hardness, c thermal insulating However, they In addition to corrosion they impart some special properties electrical properties, oxidation-resistance and Properties to the protected surface. 4.1.1 Types of Protective coatings PAINTS Paint is a mechanical dispersion of one or more finely divided pigments in a medium (thinner + vehicle). When a paint is applied to a metal surface, the thinner evaporates, while the vehicle undergoes slow oxidation forming a pigmented film.fon of a medium and film on) 2, Ventcle ( ‘iatile ‘partie high mole Tae Hatuent of tHe Pa re ad anienal lls non com Ag ° 1 21 atoll hve al dng (Coven) pow esont cave fi by the oxidation ong 3. 1 should not erack on drying. iametiony, “ey fom 2 4. It should adhere welll to the surface. ye yarticles together on the 5. Tae eaour of he pnt shoul be ale ca Tiny ld he lm : 2 Rowe tescenon ul ne el met ces petney, toughness an 7. should give 9 lossy film, HD Ty ote Bln 42.2 Constivents and thelr tunctions of @ palnt BE serarted castor ol 1. Phgment vn "eons od and elo pricing stances in te | 3, inners (0) solvents ; aint + eens Je a. volatile portion of a medium, It easily, Panaon swap er plea f te paint 1 ave colour and opty ihe Am, z Gi) ane provana swengn © te i "ty seduces the viconly of the pein, #0 that I Aid 1 pte the by reteng the desevtve Leta apiod o the sibs. wie 0. Niraves fe aprons, ee and produces io 1 inset. wether rane ofthe I seit mist Gl)” Tt increases the elasticity of the-fitm. Gv) It increases the penetrating power of the vehicle. 4. Extenders (or) fillers ‘These are white (or) colourless pigments, Functions Ik reduces the cost of the paint Gi) Te retards the setting of the pigment in all paints. Gil) Te modifies the stades of the pigments (yt prevents. shrinlage and cracking. White pigments [Wake lead GPOCO,. PHOMD. [Cithophone (75% BaSO, + 25% ZV. GD Biack pigments [Lamp black, carbon bind (Gi) Red piements [Venetian red (F305 and CaSO.) nan a FO) (“Green piemens | CheaWe, 2 Eng sty -" | Protective Coat ao 45 na» @ & 42.3 Mechariam of drying of drying oils Tale, gypsum, china ct 5 Driers These are the substances, used to accelerate the process of drying. Functions G) They act as oxygen-cariers (oF) catalysts. (They provide oxygen, which is essential for oxidation, polymerisation of drying oi. Metallic soaps, linoleates and resinates of Co, Mn-and Pb. 6. Plasticisers ‘These are chemicals added to the paint 0 provide elasticity to the film and to prevent eracking of the fm bonds dry very faster than the Triphenst phosphate, tricresyl phosphate, etc. Mechanism for conjugated of! 7. Anti-skinnini? ageits ‘The various steps involved in of conjugated oil are given below. [These are chemicals adda tothe pat to prevent gelling, es er land skinning of the paint i ‘The oil absorbs oxygen and gives ~CH=cH—cH=cH-+0,—>-cH (Graction of convened ot) ‘The di-radical again reacts with oxygen and fatty group to give peroxy and poly peroxy radicals.Potetee Contos on © © Percent paint (0 Prorprscmt po. (© Fluorescent paint ; sp Eiacen pis ere aij oy wees to Ugh Emon spr "ton eee Salt ee [phonic pot conaine snc sie ot edu sist wo small toon of colour sales fe ae a fee Bh “ts wad in TV eens advert son ns dl (© Phosphorecent paint 1 phoihorescet punt. emsin of raison eotncs for sett’ een tr ligt segped in Posptrsren sue and so er oe ke wet Dy bi. 7. PRETREATMENT OF Ti URFACES OR PREPARATION OF = MATERIALS FOR COATING Generally mesa sauces are covered with impure ike © Solvent clenaiog or degreasing _ (Srtni solvents sucha alee, mylene, asene, carton {each et. ate weed to remove ell gress sod fy ‘bites prevent ‘on the metal ue © Atal cteatng Ti reod is pany usd forthe removal of okt ‘ln outing frm te atl eric, Sluions of eas ‘Stadium phosphine wih tome, deurgens, muty ond (MEig atu are wed forthe ala Seno” Ater eslea (estan the real surace cine wi wera the with 4% sation eons ase (8) Acid cleaning or pling ==» ‘Aid cleaning i aplicible er the renova Bf cide SRR ane cer “conmion omits” edie ICL 804, HINO, tnd HPO, we wie orth procesn 9) Mechanica dening = yi st tS coer pit at renared the inechinicl cleaning such padags wits trong. poling ee (© Flame searing [his proces i doe ty puting high veloc he Mame (28 the mal sure, lr aplediofemove ta ad Tool adhering scl, ©) Sand iasting Sag ‘This proces consis of nepscing ind into ane ‘eam under th piste of 351" 16t ater i wed for removing oxi sale greene eps el race, % i {Fae Y Paring heey or 4.6 APPLICATION OF PROTECTIVE COATINGS ae ep cone wd wi et ah ere Spe osopcanuse Remus? 4.7 ELECTROPLATING = ATA Principle of Electroplating rpg or da dpe i he psy Soe mance maces “eet te poems? ‘Shemp al wees the aod ae often eee peta ta 47.2. Objectives of Electroplating © Tone te ie cro of ee ome Fe 404 Berets (4 Tope ie ea ys pect (0) Toobin spa es 4.73 Theory of Electroplating ‘Sepa es Ren tee ecg es te on ‘pind onto he rac emirate teats os Co Tissier ep lo he ip operand ate ‘Sinn abated elas etree Gis0, <= com oso ‘nang ca Co a eng een ead CO Ss cn+SoP—+ e180, 624 raat) «ae oper cong a ah cof 1208 capt ii 25 9 Fe 5D, oe shal cf te i in co em doe cig (io = OP SOP — ast rounencne hyn int rane crane eSB ee Rr oops ES Sar opi en ce i ey Fpinsttaceehovtnp onal! fae nome tosgecteed ota pat = oes 474 proces of etecropating ‘eccrine ne a oy) ee isc gem peeneig cb nal sopocan ee nema Sarde Sanath etapa ermal acre chen staf axing mt shaping Tha one slsceaf aetna ecoc en eet Go & .: it E mont arson Cnt! eS 420 oe = . re sume priest Oe roo Eis Uy ie rarecerists of Mickel ploting elon 1 EERGg Saree eu ah ay be tema 2, leroplating of ehromlum i po mbt so hen Cae ert Te ee it uaa ef bec ng 410) Th ag ce ne fee BSS sere Met ha epost RED on en os : ett Metals and Conditions 4.76, lectroplating of Some Sepik eat pp natch por ohn Soha ne’ Eh mamta e AY reer of Pe Att eng renin mes F Ha pan ie te tie Cm ath (they pee 6 Race ea wn cee Points te Remember ma «canine ie a penamann lpn eoon of met aly rh SETS ren Spee nine + Seeley ey + Spot Steen ovement ye me eee ee Soe cee ‘aces ot aamtm tog 4.75 tacos Mectng croiting + Cy ovum a nies ey Onn ean, Cin ye Steen ao aie see {fe mt ti rene yatta mtn Owns ein EE IEE Scena eee wt ce woe SNS rae gee nou mand tm fssenp bese gs me + ate he pena Dod ae soe hee ==