Corrosion and its Control LEARNING OBJECTIVES After completing this chapter, you will be able to understand the following: © Corrosion, its definition, causes and effects, | © Factors affecting rate of corrosion — primary * Types of corrosion — dry and wet (electro- and secondary factors. chemical) corrosion — and their differences. © Corrosion control methods. © Types of electrochemical corrosion — differ- * Protective coatings. ential metal, differential aeration (including waterline), pitting and crevice. + Other types of corrosion — seress, intergean- ular, microbiological, soil, erosion. + Metal finishing. * Electroplating process. © Blectroless plating. Icis estimated Cue is one of the most significant problems faced by advanced industrial societi roduced aniwally is used just co replace the rials. Corrosion c fuel systems, radiators, exhaust systems and b billion: Corrosion touches all appliances used inside and outside hom home, on the road, on the sea, in plant: and in aerospace vehicTes. Total a ansiual costs OF Hoods, Hurricanes, fir less than the costs in o corrosion. — io Corrosion in Metals and Alloys Metals are chermodynamically unstable and found abundantly in nature; so: hae they feq amautes of energy 0 get converted ino useful engineeting materials: Thus, che mecals requiting. Sane seer tendency f0 corrode, whereas those metals requiring less energy have a Tower :xamples of the former include magnesium, zinc, alur examples of the latcer include gold, silver and pl platinum Corrosion 1 a spontant action of metal oF alloy ‘vith its environment, resulting in the formation ide, hydraved oxide, carbonate, SUIphic®, sf Iphate, etc. Extraction of metals from their ores is an Iheemie process. Pure metals, being highly energetic have natural tendency to revere back to theit combined states. as _ Neat eernetion a can be defined as the destruction of my ies ie eee or electrochemical chang Metal ote =“Corction Hence, corrosi through chemiCHAPTER 10/CORROSION AND ITS CONTROL 408 + y Manel ir environment. The term ee ne of materials by chemical interaction wich their envi eri Corrosion is the det 7 ics, concrete and wood, but generally — corrosion ig sometimes also applied co the degradation of plastics, co Pie the armas ion is ii iron exposec refers to metals. The most familiar example of corrosion is rusting of iron exp © 2) *FOA() +AHLO Fe0s HOC) (Chemical composition of rust) conditi ical accack on the metal b Corrosion of metals occurs either by direct chemical attack or by electrochemical y the corrosive environment. Effects of Corrosion : The effects of corrosion are many and varied. These effects are more pronounced than the simple loss of metal as they affect the safe and efficient functioning of equipments or seructures. ae ifthe loss of metal due to corrosion is small, still it may be required to replace the expensive parts of the equipment. ‘The major harmful effects of corrosion can be summatized as follows: 1. Lass of metal or reduced thickness: This reduced thickness may lead to lack of mechanical strength, leading to structural breakdown. Sudden structure collapse or breakdown may cause hazatds or injuries to those working neat che site of the structure (e.g., bridges, cats, aircrafts). ees cal in localized areas gives a crack-like appearance to the structure. Hence considerable weakness may 7 result ffom even a'smmall amount of metal loss. ‘Times lost in making available the parts required for constructing the industrial equipme x e The value.of the goods is reduced owing to degraded appearance. ‘The fluids scored in pipes or storage tanks get Coftaminated due co chemi gets cloudy when small quantities of heavy metals -are released by : + Important Suiface properties of metals are affected. ‘These properties include frictional, bearing Propervis, ease of uid flow, electrical conductivity, surface reflectivity and heat transfer Loss of ‘echaically importane surface properties of a metallic component. 6. Mechanjpaldamspe ea sales pumps, et. or blockage of pipes by solid corrosion products. < EE fut opa Ora 4 ay * What do you mean by corrosion? * Give the chemical composition of ruse. EE corrosion Cell @ cathode, a metal lic (electronic) path be ‘ ; nan a path beeween “Providing ionic path Figure 1). A voleageailfenece between the anode and the pairs eliamny cel ae sue 7 This DC current flows from the anode through the sur- ectrlyte) to che cathode, and backer ) andlngevicment »and back to theanode throng mpleting the circuit, The corrosion current is ca aah ae ae fine che ire Path by electrons; whereas the electrolyte (anode) cor- mains uncorroded, * What ate the importance causes of corrosion? + What are the effects of corrosion? e metal receiving the, 1 receiving che current from the environment (cathode) reyROS 403_TYPES OF CORROSION 409 Metallic Path Figure 1 Schematic of corrosion cell. © Whar are the essential components in a corrosion cell? FE ies of Corrosion Dry Corrosion (Direct Chemical Attack) Dry corrosion involves direct attack of atmospheric gases on metal in che absence of moigture liquid phase, that is, conducting (aqueous) medium. The corzosive media include vapors, gases, etc. The exam~ ple of dry corrosion is che reaction between metal and oxygen (atmosphere) at elevated temperatures in perfectly dry conditions. 7 Compared to other gases and chemicals, ic is found that oxygen is mainly responsible for the corro- sion of most metallic substances. Accordingly, corrosion on nietallic surface is due to direct reaction of atmospheric gases such as oxygen; halogens; oxides of sulphur, nierogen; hydrogen sulphide and fumes evolved due to chemical reactions with metal. There are three main types of dry corrosion, 1. Oxidation corrosion (reaction with oxygen): Some mevals directly react with oxygen in the absence of moisture. For instance, alkali and alkaline earch metals reace with oxygen at room Cemperatute to form corresponding OxKes, while others FECT WIth oxyen ae higher cemperacute Noble metals such as Ag, Au and Prare not easily oxidizs ble and form an_unstable layer which decomposes soon after its formation, theteby preventing furcher corrosion “The metal-oxide layer formed.on the metals surface provects che metal against chemical action of corrosive agents. Any diffusion through chis layer of either the metal or the oxide can lead to410 + CHAPTER 10/CORROSION AND ITS CONTRC, farther corrosion. Thus, this layer plays an important role in controlling cattosion, Stable oxides of Pb, Al and Sn inhibit further corrosion by forming a.stoichiometric, non-porous, serongcadhering oxide fms. : However, in case of the oxide film is porous, atmospherr react with the metal, and the process of corrosion continues till che entir its oxide, This type of layer is formed by alleali anc alkaline earch metals. Molybdenum forms « Volatile oxide film of MoO; which acceleraces corrosion. 2. Corrosion by other gases such as Cl;, $02, HyS, NO, In dry atmosphere, these gases react with metal and form corrosion products, which may be protective or non-protective, Dry Cl, reacts with “Rg and forms AgCl which is a protective layer,-while SnCl, is volatile, In petroleum industries ac high temperacures, H1,S attacks steel forming FeS scale which is porous and interferes with normal operations. cre 3, Liquid metal corrosion: In several industries, molten metal passes through metallic pipes and causes corrosion due @ dissolucion or internal penetration, For example, liquid metal mercury dis- solves most metals by forming amalgams, thereby cOrroding them. es passing, through the pores wilt ¢ metal is converted int, _Meet Corrosion (Electrochemical Theory of Corrosion) ‘Wet corrosion usually occurs in conducting liquid (aqueous) phase. This type of corrosion occurs when the mecal comes in contact with a conducting liquid of when two dissimilar metals are immersed of

40H™ + Ifthe solution is deaerated and almost neutral, Hy is liberated along with OH™ ions. 411 2120 + 2e7 > H2+ 20H” + If the solution is deaetated and acidic, H* ions are reduced to hydrogen gas. 2H* + 2e° 9 Hp ‘The metal ions formed at the anode combine with hydroxyl ions and form the corresponding metallic hydroxide Fe(OH),, which further gets oxidized to hydrated Ferric oxide [rust]. 2Fe* + 40H~ > 2Fe(OH)2 2Fe(OH)2 + Oz + (x—2)H20 > Fez03+x-H20 us) ' = se russ ori as follows ao 3Fe(OH)2 + $02 — e304 -3H20__ a Differences between Dry Corrosion and Wet Corrosion The difference between the dry corrosion and wet corrosion are elucidated in Table 1. Table 1 Comparison between dry corrosion and wet corrosion Involves direct attack of atmospheric gases Involves electrochemical attack on metals in on metal in the absence of moisture liquid phase aqueous environments Less prevalent More prevalent ‘The corrosive media include vapors, gases, etc. The corrosive media is conducting liquid (aqueous) phase Ic is of various eypes: Oxidation corrosion, corrosion by other gases such as Cl,, SO, HLS, NO, and liquid metal corrosion Cae + What is meant by dry corrosion? * Explain briefly theory of dry corn ‘* What do you mean by wet corrosion? Icis of three types: differential metal corrosion, differential aeration corrosion and crevice cortosion * Write a note i a on electrochemical tt n, corrosion, ay Distinguish between dry and wet corrosion.CHAPIEK 1ULunne = 412-5 Wie: of Electrochemical Corrosion i res 7 3 eam rosive environment, Th while metal with high reduction poten! potential difference, che higher isthe corrosion rate. Thus, iti Corrosion ‘and cathodic metal is unattacked. EXAMPLE 1 | Consider a bimetallic couple of iron ‘and copper (Figure 3). The electrochemical eres is a5 follows: Mg (=2.52 V); Zn (-0.76 V)s Fe (0.44): Cu (0.34 V) and Ag (0.80 V). As observed, iron is placed above copper in electrochemical series. There- fore, iron is anodic to copper, that is, ir s anode and undergoes corrosion, whereas copper acts as cathode and remains unactacked. The reactions involved in the galvanic cell are as follows: Fe > Fe** +267 40 +H,0 + 2¢7 > 20H” 2Fe”* + 40H” — 2Fe(OH)2 tron | Copper Figure 3. Bimetallic couple of iron and copper. EXAMPLE 2 [| Consider a bimetallic sample of iron and zinc as shown in Figure 4. tron | Zine Figure 4 Bimetallic couple of iron and zinc. As zinc i Sa dl e foe, zinc nae EEE TAREE Soe i ne able wR. The , pewennulenre. 2 cones a, amecnn odes in contact with cope o lv wheat 2i5¢ Abd: magnesium coo tice with iron=‘The rate of ferential metal corrosion depends upon the potential difference between the s higher the difference, faster is the rate of corrosion.sa_TYPES OF ELECTROCHEMICAL CORROSION +413 EXAMPLE 3 | Consider another biiétllic Couple of steel and copper as shown in Figure >. eel Figure 5 Bimetallic couple of steel and copper. » Steel is atiddic in nacure thus undergoes corrosion (as iron is above copper in the elec- ids on the potential difference beeween trochemical series). The rate of corrosion depen: the two metals (materials). Other examples of differential metal corrosion (galvanic corrosion) include the followin, 1. Buried iron pipeline connected to zinc bar. 2. Sceel pipe connected to copper plumbing. 3. Steel propeller shaft in bronze bearing. 4. Zine coating on mild steel. 5, Lead-tin solder around copper wites, ilator Between two metals of iiaterials, ci ifference. Preventive Measures e—wVweGW“" '1. Placing a thin layer of an insu 2. Selecting materials having very less por 7: Differential Aeration Corrosion (Concentration Cell Corrosion) a oi : : iy Differential aeration corrosion occurs when @ ‘The me \ EXAI MPLE 4 | Consider a place of pure iron which is parcially immersed in an aeraeed solution of sodium chloride (Figure 6). Cathodic region Anodic region +—} Figure 6 Pure iron partially immersed in an aerated solution of NaCl.@aEs CHAPTER 10/CORROSION AND ITS CONTRO, Since cathodic reaction requires oxygen, the part of the metal exposed £0 higher oxygen concentration always acts a5 the cathodic region. The portion of the mea immersed in NaCl is anodic region. The reactions involved are as follows: : en “Anodic reaction at the lower immersed portion of metal: Fe” —> Fe +2, 1 +2 Cathodic reaction neat the water surface! 402410424” ~9 20H The examples of differential aeration corrosion include: 1. Half-immersed iron plate in aqueous solution. 2. Steel pipe carrying any liquid exposed to atmosphere. 3. Ocean going ships. 4. Steel scorage tanks. Preventive Measures 1. Using merallic coating, electroless plating or chemical conversion methods. 2. Maintaining the material’s own protective film. 3. Controlling the chemistry of fuids and using inhibitors. Waterline Corrosion Waterline corrosion is a case of differential aeration corrosion. Ocean going ships and water storage steebs tanks undergo this type of corrosion (Figure 7). The metal portion just below the waterline is more anodic co portion above the water line. Therefore, the metal just below the waterline undergoes corrosion. SS Cathodic part Waterline 40,+H,0 +26" —» 20H~ ‘Anodic part Fo—-Fe® +26" ® © Figure 7 Waterline corrosion: (a) Water storage tank and (b) ocean going ship. Waterline corrosion is common in watetlifting pipes under water. Ocean going ships also suffer fom differential aeration corrosion, Ships sunk under water for several years clo not undergo corrosion. For the portion of che shi under water, the difference in O, concentration becween the top and bottom portions of the ship is negligibly small. Thus, the ship is exposed to almost uniform concentration of ait and does not undergo differential aeration corrosion. Crevice Corrosion Crevi ‘ corrosion is often associated with a small volume of. electrolyte crapped in crevices of joints, rivets, boles, gasket surfaces, lap joints, nuts, washers or in surface deposits. Thisjo TYPES OF ELECTROCHEMICAL CORROSION . 415 cowoson occurs when oxygen cannot penetate a crevice, lading C0 st uP of a differential aeration cell. Corrosion occurs rapidly in the area with less oxygen, Also, consider the corrosion occurring when the surface of a painted metal is scratched. The scratched portion would act as a small anode, while the rest of the part would act as cathode, thus forming a local differential aeration cell. Mechanism In general, crevice corrosion occurs rapidly in the area with less oxygen. Increase in acidity and chloride content of crevice solution initiates passive film breakdown process and thereby enhances the rate of cor resion reaction. Finally, corrosion propagation continues leading to farther deterioration of the material. “The Fontana and Greene model describes crevice corrosion mechanism. This model consists of four stages. Stage 1: Corrosion normally occurs both inside and outside the crevice with the following reactions: . ‘Anode reaction: M—> M+ né- Cathode reaction: O, + 2H,0 + 4e— 40H The positively charged metallic ions ate elecerostatically counterbalanced by OH ions. Stage 2: The cathode reaction inside the crevice consumes most of the available oxygen. Stage 3: The CI” and OH ions diffuse inco the crevice +9 maintain minimum potential energy, thus forming the metal chloride. Hydrolysis of metal chloride lowers pH and MCI + #H,O > MOH), + #HCL. More M" ions attack more CI” leading to lower pH inside crevice. This accelerates the dissolucion of mecal and more M™ ions will be produced thar will further lower the PH. Stage Preventive Measures 1. Increasing resistance by using alloys that have high percenrage of chromium, molybdenum and/or nitrogen. 2. Design and fabricate to avoid crevices. Eh oe = 3. Frequencly inspecting for inadverent crevices and closing crevices by continuous welding, caulk ing or soldering. ior ‘corrosion involves localized arcack-usually in chloride medium. This corrosion arises when a small "ig eithor defective (with cracks) Or Decupied by d st/scalelsand/wvater drop. Piecing portion of che metallie surface Mechanism : ! Figure 8 shows the mechanism of pitting corrosion of iron surface in the chloride medium. The metal caer he dase deposit particle)s exposed to-lower Og concen ration and. undergoes cortosion. Once apit is formed, the rate of corrosion increases. The accelerated « jion takes place below the deposit Tammuse of smal) anadic area and large cathodic aren. Preventive Measures 1. Preparing surfaces with best postin inh eosinish sie G18 est, 2. Removing all contaminants, Tspecially free-iron by passivacion SoS 3. Designing and fabricating co avoid crappedrimpooled liquids,é CHAPTER 10/C {SION AND ITS CONTROL HA yCORROSION Fot! + 20H —" Fo(OH)e. Corrosion produot id d Moro oxygonator Moro oxygonatod ig desir cathiodo sm font 2or—+ 20H = measures for gal- ~ Write importane preventive vani¢ corrosion. «What do you mean by waterline corrosion? «Explain che mechanism of picting corrosion? © Write a note on crevice corrosion. «Explain differential mecal corrosion. + Iron corrodes in contact with copper, but not with zine, Justify. © How do you prevent differential metal corro- sion or galvanic corrosion? Other Types of Corrosion Jiress corrosion! Mechanical Ges within de mee bring abou ees onion ‘The incernal esa ela on the metal is TIDJECTEN TS Mechanical operatzons such as pressing, ham- Henne, bendTaE Welding ot riveting. The ses canalso be extSERELSeress That acts on the metal Turing service conditions, The metal atoms under stress ate always a highs energy Teves tom pared 0 geressffee atoms. The stressed part of che metal, therefore, becomes more reactive than, the stress-free part. As a result, a galvanic cells Tormed with the stressed pare acting as anode, and Stress free part acting as cathode (Figure 9), Under specific corrosion environments, the stressed part undergoes corrosion, initiating the crack. In ehe presence of continuously acting seress and cor osion medium, the crack pfopagates through the metal. Cencking of brass and caustic embrictle- ‘ment of steel boilers are two examples of stress corrosion, Cathode node Figure 9 Stress corrosion in metal, Seasonal cracking: This type of corrosion was firse observed dling che B ing che monsoon season, Due to diminished m s cicish eulein India dur- itary activity during chis season, brass carcridges were stored for later usage. Afeer Usage, After some time, it was found chat cracks were developed on chePES OF 95 OTHER TY! F CORROSION © 417 surface of these cartridges. The seasonal cra like copper and its alloys 1g occurs due to the action of (a) susceptible agent 1 4 (b) attacking agent ike ammonia and (c) tensile stress (residual). Caustic embrittlement of steel boilers: Mild steel boilers undergo corrosion at the stressed portion when the operating pressures are between 10 atm and 20 atm. Fine Gracks may develop at the stressed portion of the boiler, Boiler water containing alkaline impurities pass into these cracks by capillary action, This water evaporates and leaves behind caustic soda in the cracks, whose concentration tus increases. Thus, a galvanic cell is set up between the iron under stress and the iron in the main body. The cell can be represented as follows Tron Cunder stress) ‘Conc NaOH} (in the cracks) Dil NaOH | Iron Cin boiling water) (main body) Iron under stress acts as the anode and gets corroded resulting in boiler ‘itu RSE at high temperature to give NaOH. NajCO3 + H,0—5 2NaOH + CO2 The NaO .d flows into hair-thin cracks and crevices. ‘There it reaces with’ iromand forms i ae €) which decomposes to give Fe;O4 and NaOH. 2NaOH + Fe—> NazFeO + Hz 3Na2FeO2 + 4H30 — Fe304 + 4H2 + 6NaOH NaOH thus formed, further reacts with iron to cause corrosion. This is called caustic embrittlement. Preventive measures «Applying protective coatings. * “Using corrosion inhibitors. «Performing stress-relief heat treatments. + Reducing the overall stress level and designing out stress concentrations. + Adding Na,SO, to boiler water in addition to cannin and lignin to boiler water to prevent caustic cracking. i - Mis 2. Intergranular corrosion: Generally observed in alloys, chis corrosion involves an attack on the rain boundaries of a meral or alloy, where the formation of a corrosion product takes place. This corrosion is not observed externally, and leads co sudden unanticipated failure of the material. For ‘estance, when stainless seeel (18% Cr, 8% Ni) containing more chan 0.19% enrbon is heated to high erpperacure and cooled slowly or held at 650°C fora shore incerval of time, a rapid reaction cere beeween carbon and chromium, Chromium carbide, chus formed, precipitates at che grain boundaries and results is: che formation of galvanic cells (Figure 10), Chromium-rich grain centers act as the cathod undergo corrosion. This eype of corrosion is als while che grain boundaries act as anode and called grain-boundary corrosion, Preventive measures © Selecting an alloy type resistant to intergranular corrosion, * Avoiding heat treatments or service exposure that make che matetial susceptible. Normally, this occurs with austenitic stainless steels when chey are held for sometime in the sensitizing temperature range of 470-915°C «Applying protective coatings.40.5. FACTORS INFLUENCING RATE OF CORROSION 419 (eteicclehs a (lle «Explain caustic embricelement in boilers * Write important preventive measures for the following types of corrosion: (a) stress corrosion and (b) inter granular corrosion. + Explain very briefly soil corrosion and erosion corrosion. ‘Write a note on inter granular corrosion. + Explain microbiological corrosion. ‘actors Influencing Rate of Corrosion ‘There are ewo factors influencing the rate of corrosion: Primary factors related co the metal and second- ary factors related to the environment. Primary Factors Nature of the metal: The tendency of metal to undergo corrosion depends on its nature. Metals with low seduction potential exhibit high seactiviey, and hence are more susceptible for undergoing cottosion. Thus, the tendency of a metal to undergo corrosion decreases with increase in reduction potential (galvanic porential). Metals such as Li, Na, Mg, Zn. etc., have low reduction potentials and therefore undergo severe corrosion in cortosive environment, The noble metals wich high reduction potential, such as Ag, Au, Pr, etc: are less susceptible for undergoing corrosion. However, few met- ls deviate from the normal tendency, due to their ability to develop passive layers. Electrode potential difference: Potential difference becween the anodi id ‘cathodic regions is known as open-cifcuit potential difference. Larger the open-circuit potential, higher is the rate of conosion. For example, the porential difference Between iron and silver i§ 1.14 V, which is more ‘han 0.3 V between iron and tin. ‘Therefor, iron corrodes faster when in contact with silver than ‘with tia, Thus, farcher apart che metals stand from each other in the electrochemical series, greater isthe incensity of corrosive attack on che anodic metal. On this account, the use of dissimilar met- als should be avoided wherever possible, 3. Surface state of the metal: Seate_or condition of the surface of che metal affects the corrosion process rate. For example if part of the surface is, covered by oil or dust particles then severe pit ng co i the metal surface. Corrosion atthe susface is also aceeTerared By presence _ ting corrosion occur c of water droplet on the surface. Heterogeneity at the surface of the metal results in high corrosion rate. k 4, Hydrogen overvoltage: In most of che electrochemical reactions, the competing cathodic reaction 5 st of the elee ee is the hydrogen ion reduction (0 liberate hydrogen gas. Hydrogen overvoltage is the measure of the” aes dleney of che elecerode to bette hydronss ‘gas. A metal with low hydrogen overvoleage on its «Bee ee asbre SESEEpUIBTE for corsoniOo- LOW BYTE overvoltage results in faster cathodic regc- ne anodie reaction rae, and hence increases che overall rate of corrosion. Fetus by metals: A few metals exhibie che tendency co develop passive, ry on exposure to corrosive mediuim. The nacure of such a passive layer but protective films of jaye! pol ee nerve FAS OF ZF corrosion. The passive layer sully meal oxide formed onthe surface of the metal is stable, highly insoluble with low conductivities. This allows it co act as a protective eee comrsion. Metals like Al, Tiand Gr develop such a layer on their surface, tion. This even increases 5. Formation of protective layer and prevent and become passive £0 corrosion:CHAPTER 10/CORROSION AND ITS CONTROL 420 ide layer is unstable; so On the other hand, if the oxide layer i ; ese corr For example, metal ox! erosion continues co cakes place. le corrosion, as they are porous nd cannor complecely prevent acc ess to the corrosive environment, Secondary Factors rrosion medium, ever, nietals like AL, Zo curs even in abse corrosion occurs ce of air due to the continuous evolutiva of region. se iain ier 2, ‘Temperature: The rate of any chemical’réaction increases with rise in’ temperature increases the conductance ofthe medium, reduces increases the rte of corrosion, £ corrosion is greatly influenced by the relative sizes ‘Anodic and cathodic area effect: The rate of SS . coated iron material wi cathodic region then, leads corrosion effective. For example, ti the surface where tin is cathodic to iron (Figure 11). Large cathodic area a pe j— Sn ‘Small anodic area -}— Fe [Anode] High rate of corrosion of iron Figure 11. Small ratio of anodic co cathodic region leading to high rate of corrosion. fa }— Zine 7— Fe [Cathode] ‘Small cathodic area Low rate of corrosion of Iron Figure 12 Large cati Teading 'ge ratio of anodic to cathodic region leading to low rate of corrosion, Se ea d porous, then ide layers of Fe and Zn cannot Control higher is the corrosion race. At pH > 10, : ser the pH of the co ie : t . pH In pene, lowe Bo maton of a protective contng of hydrous oxi. How. aS Sree er caresion in highly alkaline sofuion. Ifthe pH < 3, severe f hydrogen at the cathodic ture. Increase in passivity of the metal, and thereby of anodic and cathodic ateas. When the tio foe ele tion Sa het is, smaller anodic region and larger id inténsive anodic reaction, chus making, the overall ith some pinholes or uncovered areas onFACTORS INFLUENCING RATE OF CORROS! F JON - 421 4, Polarization of electrodes: Pola ic equilibrium values, that i it sit a polarization at at Bots i e a ircuit potentials causing a de re Ee Ose oe ectrodes is due to conc i i Fe orential ntration changes in the electrode region. It sae : te i the cathode to become more anodic and thae of anode to become more cathodic. ions must go in-step with her if be ‘ned, The ovel go in-step with one another i corrosion is to be serine 7 pose of electrochemical corrosion may be principatty governed ether OY anodic or by 2 eaction rate, For metals such as Feand Zi in aqueous solution, ehe race of Coe d (cathode polarization) jn which corrosion cutrent is under cathodic control. If che anodic reaction is the rate determining step, then the race ‘of corrosion is controlled by anodic polarization. Figure 13 shows the polarization curves for corrosion processes proceeding by (a) cathodic control, (b) anodic control and (c) mixed control. Cathodic Cathodic Cathodic ave +e ye Potential; Potential Potential ip Anodic| ve Anodic Anodic a —ve Current Current Current (a) (b) © Figure 13 Polarization curves: (@) cathodic control, (b) anodic control and (<) mixed control. In chese diagrams, the polatization curve has a steePer slope for che electrode that is polarized to a greater extent. 5, Gonduceance of the medium: Corrosion is at electrochemical reaction, which involves electrons : eee one transfer (conduction). The presence of conducting species in the acmé ere increase the corrosion rate. This rate is more in a wet atmosphere ( conducting) than in the dey atmosphere. fe (sore CO etapa j ee rte 6. Humidity: Race of corrosion is low) se crjarive humidity Te increases with increase in humid sey up toa cercin valu call Le aay “fumidiey; bue corrosion abrupely increases above critical wumidity. eee en a: * Explain how the following factors influence * Pin holes on cin-coated iron macerials are most corrosion rate: (a) nature of the corrosion, prod~ ,_isastrous co iron than pin holes on zine-coated sernd doy surface state of #3 metal, iron materials, Justify the stacemenc, * What is hydrogen overvoltage? How does it ¢ Which of the following ewo condicions favor Mle cenevign ence in acetal? corrosion rate? Justify your answer. © Whar is the effect of pH and temperature on a. High ratio of ‘anodic co cathodic areas. reece ae cevoaion? b, Low ratio of anodic co cathodic areas. * Write a note on polarization of electrodes in corrosion cell. mmmJON AND ITS CONTROL preR 10/CORROS tae retention of moiscure should version ean be reduced by eRe USE inavoidabl id be placed between 0 i; on the relacive sizes 0 positioned in the galvan dissimilar mecals- anode and cathode. Smaller anode and i Corrosion Control Methods 7 ; I ni in ‘a metal is natural Corrosion control is more realiseic chan corrosion prevention ee any iia ae ae biti by which metal is converted into a more stable men ace Te eae COTOION trol techniques as the corrosion depends on che nature of environment: PS ‘ontrol ethods are discussed in the following sections: 1s ection: i any design, che greaeer che number of angles, comers edges and sane pe mote | irate ie becomes fr efcient surface of ment Hence 8B #5 Ossi»? ~ and U-shaped i profiles in construction should be minimized (Figure 14). : ei } * No corrosion occurs without the presence of moisture. The design of a seructure s! ould be such | be as low as possible. ofa single. metal rather than dissimilar ic series should be + Differential metals. If their use is Uf used. An jnsulacor shoul le, metals closel} «The rate of corrosion depend: | larger cathode should woided as far as possible. Good design Poor design Weld | Weld Water does not collect Water collects Figure 14 Design selection for corrosion control. 2, Brosective coatings used tc jatings: These are used to i ‘coatings include m Sea eine atings etallic coatings, chemical conversion coatings, ceramic coatings and ofgenic outings. 3. Gal proto: in ; The corrosion of metal Bree : cakes — cathodic region, met is unaffected. The principle a the anodic region wherens * the pee e eliminat is can be achieved by P*O% of anodic sites and conversi of nei ea eee in en soutce so that the specimen always remains cathode. This technia' a le. This eechoi cai ng lecras of offering protection to a speci from a specimen a Si source is called cé ic i Pa be achicha i P : I Pines ate fs nde eo In cis mesh he meal sete is coi aia chode bY into "a 7 ri into a cat meee a a ich acts as an auxiliary anode. The sepet comme use . These metals being more active, acts as anode ‘and unders? Faww coRROSION GONTROL METHODS + 423 eferential corrosion, thus protecti ae chu pe receing the metal structure, Since the anodic metals are sactificed nt nae, this method is known as sacrificial anode method, New auxiliar se at ificial anodes as and when required. For example, i nae nected to underground pipelines. : (9 Mapes sare fixed to the sides ofthe ships 5 ‘rent method: Anothi i apre a ier method, _direet current larger than te cotros See eT : ion cuttent, The protected metal is ne gative terminal of a DC source, Positive terminal isc ke Graphite. TI : ‘onnected to an inert anode like Graphite. The metal structure being cathode, does not undergo corrosion (Figure 15). rotection is by applying a ‘made cathodic by connect- structure Inert anode Figure 15. Impressed current method. che prevention of corrosion by impressed anodic .w metals like Ti and alloys like steel, when ma -made as ‘anode exhibits passivity by forming their oxide layers. In case of met Te: dich as ‘Ti, Ni, Cr and their alloy , application of Lene suitable anodic current makes them, ‘and decreases their rate of dissolution. The potential re- quired to protect the metal can be vPeained from porential-cusrent curve as shown in Figure 16. anodic protectio Potential ipo‘ Log —> Figure 16 Potensal-currene Cun: i current also i ‘As the potential is increased isl fe current al tion of metal. This trend ‘continues until che current reaches * cricigal value due to the development ‘of oxide layers sets In ‘This porential is ca ‘ ‘Above Ep, the ctrsene fiw decreases an reaches am num valu called che passivacing current Albowe py the enum provective curreny nsity co maincain passivation. TE che porencial is fur- jp. Te is the minimum prover vor increased, che metal remains © cil «particular poten is reched (line CP This potential range in which anodic prot an be achieve is ccalled protection range.CHAPTER 10/CORROSION AND ITS CONTROL 424 + «char it requires a small current. However, the corrosion rate cannot - al oe a ia ieee A drawback of the method is a siege Ee bas ied th that do not passivate. This method of anodic protection 1s utilized in portation d acids. 5. cones bitors: These inhibitors reduce corrosion by re reactions. ci * Anodic inhibiors: Anodic reaction is the oxidaci fe mation of Pe" ion of ton, Fe fons ae formed a an aes cion process. "This i achieved by the addlcion of (anodic reaction), and thereby retard che corrosion process. Fo aap ia anions such as chromate, cungstate, molybdate, etc., which combine ae ae at anodic region, forming sparingly soluble salts. These sales are deposited on the anodic sites, forming protective films, which acts as barriers between metal surface and corrosion medium, ‘prevent further anodic reaction and hence corrosion. arding either anodic or cathodic of mietal, hae is, for example in rusting prevent fu ee + Cathodic inhibitors: These act by inhibiting the cachodic reactions which involve the liberation of hydrogen in acidic solutions and OHT ions in alkaline solution. These can be of two types: " (a) Organic cathodic inhibitors such as amines, mercaptans, thioureas, sulphoxides, form a pro- tective layer on cathodic regions, prevent the evolution of hydrogen; thus decreasing the rate of corrosion. Eee (b) Inorganic cathodic inhibitors such as sulphates of Mg, Mn, Niand Zn are used in neutral or alkaline medium, These inhibitors react with OH™ ions liberated at cathode, forming insol- uble hydroxides, which form protective film over cathodes areas and prevent corrosion. Concept Check \ * What are the important preventive measures taken during initial design and material selec- Explain impressed current method of corrosion tion for any structure? cael: uccure * What are ion inhibi i elyiar astra : : corrosion inhibitors? Explain the Mrethod af principle of cathodic protection action of anodic and cathodi ion inhibi of corrosion concro? fs jodic corrosion inhibi- * Explain sacrificial anode protection method. apt serie a * Explain anodic protecti é ction method of corrosi control. persion