1 Corrosion and Its Control ilizations, like empire, fall not so much because of the strength of the enemy outside as through the weakness and decay within” 1 INTRODUCTION Corrosion is the process of gradual deterioration of a metal from its surface due to the unwanted chemical or electrochemical interaction of metal with its environ- ment. For example, formation of a layer of reddish scale of hydrated ferric oxide on the surface of iron, also known as “rusting of iron”. 1.2 Cause of Corrosion Metals exist in nature in the form of oxides, sulphides, sulphates and carbon- ates. These chemically combined states of metal known as ‘ore’ has low energy and is thus thermodynamically stable state for metal. A considerable amount of energy is required during metallurgy. The extracted metal (in the isolated form) has higher y and thus it is thermodynamically unstable state. Thus it is the natural tendency of metal to go back to the thermodynamically stable state. Metals do this by interacting chemically or electrochemically with their environment to form surface compound and thus undergo corrosion. Metallurgical Operation Environment Ore of Metal ———————>_ Pure metal ————> Corroded Metal (Thermodynamically + Energy (Thermodynamically (Comparatively stable state) unstable state) More stable than, pure metal) Although corroded metal is thermodynamically more stable than pure metal i but due to corrosion useful properties of a metal such as malleability, ductility and electrical conductivity are lost. 1.3. Effects of Corrosion Effects of corrosion are briefly given below : (@)_ Loss of useful properties of metal and thus loss of efficiency, (®) Decrease in production rate, because efficiency is less and replace- ment of corroded equipment is time-consuming, (©) Increase in maintenance and production cost, and (@ Contamination of product. (CS)cs2 CT ~ 7A CHEMISTRY TYPES AND MECHANISM OF CORROSION 2 2. Chemical or Dry Corrosion When metal surface is in immediate proximity to atmospheric gases or anhy- drous liquid, a direct chemical interaction between the two leads to chemical or dry corrosion. It is of following three types = (a) Corrosion by O, (Oxidation Corrosion) It generally takes place in absence of moisture via 2M+n0, ——> 2M"* + 210? ——>M,0, Metal ion Oxide ion Metal oxide At low temperatures, alkali and alkaline carth metals are oxidised and at high temperatures, except Ag, Au and Pt, all other metals get oxidised. A thin layer of oxide formed at the surface of metal can be (i) stable, impervious and tightly-adhering, like the oxide films on Cu or Al, it acts as a protective coating and thus further corrosion is prevented. (if) unstable and decomposes back to metal and oxygen. That's why Ag, Au and Pt do not undergo oxidation corrosion. (ii) Volatile, the moment it is formed it gets volatilized and metal surface again gets exposed for further attack leading to continuous and rapid corrosion. Forexample, 2Mo+302——+ 2Mo Oa volatile Hence Mo undergoes excessive corrosion. (iv) Porous, hence further attack through cracks or pores continues and hence the corrosion continues till the entire metal is converted to metal oxide. Pilling-Bedworth rule The smaller the specific volume ratio { = Yume of metal oxide | tor is volume of metal |’ 8°" med will be porous, through which ‘orrosion. tios of W, Cr and Ni are 3.6, 2.0 and 16 the rate of corrosion of W is least, even at higher the oxidation corrosion, because oxide film fo: oxygen can diffuse and bring about further c For example, the specific volume ra respectively. Consequently, temperatures. (1) volume of the oxide 2 volume of the (11) Volume of the oxide < volu and strains and hence cracks and Parent metal => non-porous or me of the parent metal, oxide layer faces stress Pores develop in its structure. Consequently, rate of oxidation and 4 in case ) and rapidly increases in ease (I) sation corrosion decreases to 227° Examples of metals which follow case (1 i ) are Al or Cu and Examples of metals which follow case (Il) are Li, Na, Kand Mg.CORROSION AND ITS CONTROL haa Mechanism of Oxidation Corrosion Metal gets oxidized (M ——4 M"* + ne”) and electrons so released lead to A 1 a the reduction of O, (30, +2e——» 0?-). Formation of métal oxide (M; O,) takes place at the point of meeting of M"* and O?~. The resulting metal oxide scale forms a barrier to restrict further oxidation. As the size of M"* is much smaller than that of O°, hence faster outward diffusion of metal through the scale leads to continuation of oxidation, provided metal oxide barrier is sufficiently porous. It is tobenoted that slow inward diffusion of O?~ through scale also takes place because size of O* is large and hence its mobility is also less. (b) Corrosion by other gases Depending on the chemical affinity between metal and gas and the formation of protective or non-protective layer on metal surface, some gases like Cl;, H, Sete. exert corrosive effect to different extent. For examples, (i) 2Ag +Cl, ——> 2 AgCl AgCl film is protective and thus protects the metal from further attack of chlorine ‘on silver. (ii) Sn +2 Clh—> SnCly, SnCl, film is volatile and hence Sn undergoes excessive corrosion. (0) Liquid metal Corrosion Liquid metal corrosion occurs when liquid metal is allowed to flow over solid metal at high temperature. It leads to weakening of the solid metal due to (i) its dissolution in liquid metal or (i) penetration of liquid metal into solid metal. For example, coolant (Sodium metal) leads to corrosion of cadmium in nuclear reactor2.2 Electrochemical or Wet Corrosion It takes place mostly under wet or moist conditions through the formation of short-circuited galvanic cells. Wet corrosion is more common than dry corrosion. Electrochemical corrosion involves : (i) Separate ‘anodic’ and ‘cathodic’ parts /areas between which current flows through the conducting medium (ii) Occurrence of oxidation (corrosion) at anodic areas which generates metallic ions, (iii) Non-metallic ions like OH ~ or O?~ are formed at cathodic areas, and (iv) Diffusion of metallic and non-metallic ions towards each other through cénducting medium and formation of corrosion product somewhere between anodic and cathodic areas. For example, Rusting of iron in neutral aqueous solution of electrolyte in the presence of O, or in acidic environments with the evolution of hydrogen. Fe2* ions originate at anode and OH ions originate from cathode. Smaller Fe?* ions diffuse more rapidly than the larger OH ions, so corrosion occurs at the anode, but rust is deposited near cathode. The electrons released at the anode are conducted to the cathode and are responsible for various cathodic reactions such as (i) Oxygen absorption. In the presence of dissolved oxygen (@) inacidic medium : 4 H* +02+4¢ 3 2H20 (b) in neutral or weakly alkaline medium : 2H20+0O2+4e¢ > 4OH™ (ii) Hydrogen evolution. In the absence of O, (@) in acidic medium 2 Ht +2¢ > H2 (b) in neutral or alkaline medium : 2 H2 O +2” > H2+2 OH”A TEXT BOOK OF ENGINEERING CHemistay css is e cathode, metal ions collect the electro; (iii) Electroplating. TS nS and get deposited on the cathode ee Cu +2e° > Cu 23. Comparison of Chemical Corrosion with Electrochemical Corrosion [ sno. | Chemical Corrosion Electrochemical Corrosion 1. | Itoccurs in dry condition. It occurs in wet condition (in the | presence of electrolyte or moisture) | 2._ | Itinvolves the direct chemical attack of | It involves the setting up of a large the metal by environment. number of galvanic cells. 3. | It is explained by absorption | It is explained by mechanism of | mechanism. electrochemical reactions. 4. | It occurs on both homogeneous and | It occurs only on heterogeneous metal | heterogeneous surfaces. surface. 5. | Corrosion is uniform. Corrosion is not uniform, if the anode | area is small, pitting is more frequent. 6 | It is a slow process. It is a fast process. 7. | Corrosion products accumulate at the | Corrosion occurs at the anode, but | same place where corrosion occurs. products accumulate near the cathode Example 1. What are the various factors that contribute to the rusting of iron ? Solution. The various factors which contribute to the rusting of iron are summarized below : * Both oxygen and water are essential for rusting (This is because iron will not rust in dry air or in water that is completely free from oxygen) ° The rust formation is also accelerated by te (i) the presence of acids and electrolytes ; (ai) the contact with less reactive metals like copper and (iii) rust itself. 24 The Types of Electrochemical Corrosions 24.1 Galvanic Corrosion It takes place when different metals are in contact and jointly exposed t corrosive atmosphere. The metal which is higher up in the electrochemical series, with more negative electrode potential will form anode and undergo corrosion. For examples, Zn and Cu ; Zn and Ag ; Fe and Cu constitute galvanic couples. In the Zn-Cu galvanic cell, Zn behaves as anode where oxidation and corro- sion occurs and Cu behaves as cathode and is protected. Galvanic corrosion can be minimised by () Avoiding galvanic couple, (i) Providing an insulating material between the two metals. Example 1. Differential metal corrosion (DMC) is also known as ‘galvanic corrosion. True or false ? Solution. Truesee Sono 242 Pitting Corrosion = Consider a dr chis a drop of water resti which is covered by the cares on the surface of metal. The metal surf: lo . The metal surface Ww an anode and suffers corrosion, th oxygen concentration {O,] and thus acts as as cathode. , the uncovered metal surface, due to high (O,] act ‘ ),] acts — Oxidation of ” ‘dation of + Fe(OH), oN Drop of water OT +40 rte” . Fig. 4, Pitting Corrosion. Atanode : Fe pel 426° At cathode : 30,+H,0+2¢ ——> 20H Oxidation Fe" +2 OH” —> Fe (OH); ——— Fe (OH)s Formation of small anodic and large cathodic areas set up differences of potential at localised spots to pit, this produces corrosion current. Pitting of the eevtal occurs when there is a break in the protective layer. Pitting corrosion is a rane iniform corrosion resulting from a localized accelerated attack and results in the formation of pits, cavities and pin-holesin the metal. Once a small pit is formed, the rate of corrosion will be increased. 243 Crevice Corrosion ra crevice between different metallic objects, ¢-8-- bolts, nuts, rivets, Conside etc., in contact with liquids. Crevice area has lack of oxygen and thus becomes anodic region. The exposed fe at anode. Crevice corrosion is thus Corrosion takes plac tion of two metals exposed toa corrosive environment areas act as the cathode. accelerated attack at the junc! Cathode Crevice area Fia. 5. Crevice corrosioneas) A TEXT BOOK OF ENGINEERING CHEMisTay Concentration cell corrosion or Differential aeration corrosion It occurs when a metallic surface is partially immersed in an electrolyte and partially exposed to air. 2.4.4 Cathode XN Zn rod Electrolyte (NaCl) Fig. 6. Concentration cell corrosion. Poorly oxygenated metallic part becomes anodic and undergoes oxidation. ‘ Zn —— Zn"? +2€ Well oxygenated part becomes cathodic. At the cathode, O, takes up electrons to form OH ions $O,+H, 0426 > 20H The Zn?* and OH ions interact to give Zn (OH), Thus, corrosion occurs at anode. 2.4.5 — Water-line Corrosion The concentration of O, above the water surface is greater than that under the surface, when water is stagnant in a steel tank. This generates an oxygen concen- tration cell. In this cell the metal just above the water level is cathodic w.r.t. the metal below the water level. Corrosion occurs at the anodic part, the metal just below the water level. The cathodic area is completely unaffected by corrosion. Cathodic part = Steet tank Anodic part Water Fig. 7. Water-ine corrosionCORROSION AND ITS CONTROL CSL At anode : Fe ——> Fe™+2e Atcathode: 4H* +O, +4e” ——> 2H, O ——> 2H*+20H™ Net : Fe’* +2 OH ——> Fe(OH); If the water is relatively free from acidity, little corrosion takes place. When marine plants attach themselves to ocean going ships, water line corrosion is often accelerated and for its checking, use of antifouling paints is must.3 PASSIVITY OR PASSIVATIO! Passivation is the phenomenon by which a metal or alloy shows high corrosion resistance due to the formation of a highly protective, very thin (about 0.0004 mm thick) and quite invisible surface film. Passivation of metal takes place only in certain environments, which tend to maintain protective film on the surface. For example, Ti, Cr, Al and Cr containing stainless steel alloys exhibit outstanding corrosion resistance in the presence of oxygen. This is due to the formation of thin, protective oxide film on their surfaces. Whenever any damage occurs, this film is automatically repaired in oxidising, environments. But in reducing environments, the passive metals and alloys become chemically active and are rapidly corroded. Examples : Aluminium is not attacked by concentration HNO, but iron gets -rapidly corroded even by dil. HNO. In contrast, stainless steel, due to the presence of Cr in it, maintains protective oxide film so exhibits high corrosion resistance in HNO, solution over a wide range of concentrations.CORROSION AND ITS CONTROL css 4 GALVANIC SERIES Passivation makes effectiv: e electrod so they act cathodic and exhibit n : to that predicted by the electroch Potentials of some metals more positive cble behaviour. This behaviours exactly opposite cs 2 iemical series. Consequent! called galvanic series have been Ne real ai ameral ! prepared which gives real and useful information regarding the corrosion behaviour of metals and alloys in a given environment. Galvanic series : Mg, Mg alloys, Zn, Al, Cd, Mild steel, Cast iron, Solder, Pb, Sn, Anodic (Easily corroded) Cathodic (Protected) Pt, Au, Ti, Ag, Cr, Stainless steel The following points should be noted regarding galvanic series : Galvanic series predicts the corrosion tendencies of both metals and non-metals in actual environments. But electrochemical series predicts the relative displacement tendencies of metals and non-metals in electrolytes containing particular concen- trations of salts of the same metal that was being studied. In Galvanic series, electrode potentials are measured by using calomel electrode as reference elec- trode. In contrast, in electrochemical series, electrode potentials are measured by using standard hydrogen electrode as reference electrode. In galvanic series, the _ position of metal alloy is different than that of pure metal. 5 FACTORS INFLUENCING CORROSION Rate and Extent of Corrosion Depends on ae Nature of the metal Nature of the environment lo. 1. | Purity of metal, Temperature, 2. | Physical state of the metal, Humidity, 3. | Nature of the oxide film, Effect of pH, 4. | Position in the Galvanic series, Nature of electrolyte, 5. | Relative areas of the anode and cathode | Conductance of the corroding medium, i tof corrosion, | Formation of oxygen concentration cell, | 6. | Solubilities of the product o| coe peer atmosphere , | 7. | Volatility of corrosion products, Presence of impurities in atmosphere 5.1. Nature of the Metal Let us discuss first, how rate and extent of corrosion depends on the nature of us , the metal : metal. Lesser is the percentage purity of a metal, faster is the rate = (i) Purity of s 2 of Beas ‘example, in the case of Zinc metal : % Purity 99.999 99.99 I 99.95 { 99.0 sooo | 7,200 Corrosion rate 1 2650 |css A TENT BOOK OF ENGINEBRING CHEMISTRY The umpunties present in a metal cause heterogeneity and thus tiny electro chemical cells are set up at the exposed part of the impurity and corrosion of metal around the impunty takes place due to local action. Thus it is clear that corrosion resistance of a metal can be improved by increasing its purity and pure metals are generally corrosion resistant. (i) Physical State of the Metal. Physical state of the metal means orientation of crystals, grain size, stress etc. The larger the grain-size of the metal/alloy, the smaller will be its solubility and hence, lesser will be its corrosion. Areas under stress, tend to be anodic and corrosion takes place at these stressed areas. For example, caustic embrittlement takes place in stressed parts such as bends, joints, rivets, ete. in boilers. (ii) Nature of the oxide film. The smaller the specific volume ratio me of metal oxide ‘olume of metal ( } greater is the oxidation corrosion, because oxide film formed will be porous, through which oxygen can diffuse and bring about further corrosion. For example, the specific volume ratios of W, Cr and Ni are 3.6, 2.0 and 1.6 respectively. Consequently, the rate of corrosion of W is least, even at higher temperatures. (iv) Position in the Galvanic series. The greater the oxidation potential, when the metal is higher up in the galvanic series, greater is its tendency to become anodic and hence greater is the rate of corrosion. Thus, the extent of corrosion depends upon the position of the metal in the galvanic series. When two metals are in electrical contact, greater is the difference in their positions in the electrochemical series, faster is the corrosion of anodic metal. (v) Relative areas of the Anode and Cathode. The rate of corrosion of metal is less when the area of the cathode is smaller. When cathodic area is smaller, the demand for electrons will be less and this results in the decreased rate of dissolution of metal at anodic regions. Cathodic area Anodic area For example, a small steel pipe fitted in a large Cu tank undergoes localized, rapid and severe corrosion. (vi) Solubility of corrosion products. Insoluble corrosion products function as physical barrier, thereby, suppresses further corrosion. But if the corrosion product is soluble in the corroding medium, the corrosion of the metal will proceed faster. For example, Pb in H, SO, medium forms PbSO, which is insoluble in the corrod- ing medium (H,SO,), hence corrosion proceeds at a smaller rate. In general, Rate of corrosion of anodic region (vii) Volatility of Corrosion Products. Excessive (rapid and continuous) cor- rosiont of metal takes place if corrosion product is volatile. This is due to the fact that as soon as corrosion product is formed, it volatilizes, thereby leaving the underlying metal surface for further attack. 5.2 Nature of the Corroding Environment (i) Temperature. The rate of corrosion increases with rise in temperature. This is due to the fact that the anodic attack by the anions, the cathodic evolution of hydrogen gas and solubility of O, decreases with rise of temperature.CORROSION {ORROSION AND ITS CONTROL csa7 As Lip eeete at pans areas behave as anode, so corrosion due to differentia) F ets slowed down at higher te : Fasion of ©; into pits and crevices. igher temperatures. This is due to faster diffusio pine ae embrittlement takes place only at higher temperatures in high pres- Similarly, intergranular corrosion takes place at higher temperatures. (ii) Humidity. The greater is humidity, the greater is the rate and extent of corrosion. This is due to the fact that moisture acts as a solvent for O,, Hy S, SOz and NaCletc. to furnish the electrolyte essential for setting up 4 corrosion cell. _ For example, (a) Atmospheric corrosion of iron is slow in dry air compared to moist air. (b) Gases like Hy S, SO, etc. increase the aci jin water and hence increase the corrosion rate. (c) Dissolution of NaCl in water leads to the increased conductivity and thereby increased corrosion rate. (iii) Effect of pH. Corrosions of those metals which are readily attacked by acids can be reduced by increasing the pH of the attacking environment. For example, corrosion of Zn can be minimised by increasing the pH to 11. In general, acidic media are more corrosive than alkaline and neutral media. The Correlation between pH and corrosion can be obtained from pH-potential (Pourbiax) diagram. (iv) Nature of the electrolyte. The nature of the electrolyte also influences the ty of mediumby their dissolution rate of corrosion. (a) Anions. If the electrolyte consists of silicate ions, silicates and prevent further corrosion. If the electrolyte consists of chloride ions, they destroy the protective film and the surface is exposed for further corrosion: For example, rapid corrosion of Al in sea water. they form insoluble (b) Cations. Corrosion of many metals is rapid in presence of NH,’ ions in corroding media. ; (c) Conductance of the corroding medium. The corrosion current depends upon the internal resistance of the short-circuited cells which in turn depends on the conductance of the electrolytic medium. If the conductance of the soil is more, the corrosion of underground structures will also be more, consequently there will be snore severe damage to the metallic structures in the presence of stray currents from power leakages. Noie, Conductance of clayey and mineralized soils is more than that of dry sandy- soils hence corrosion of underground metallic structures is more in clayey and mineralized soils. (0) Formation of oxygen concentration cell. Due to differential aeration, “0x- ygen-concentration cell” sets up and anodic part having less oxygen concentration yn. For example, (a) Crevice corrosion and (b) Waterline corrosion suffers corrosio! q A occur due to the formation of differential-oxygen concentration cell.2.7.2 Stress Corrosion Metal components are subjected to uneven stresses during their mare tur- ing process which involves cold working, quenching, bending, pressing or heat treatment. Areas under stress act as the anode and other areas act as the cathode The electrode potential thus varies, and lead to corrosion. Stress Corrosion is acceleration of corrosion in corrosive environment. Thus for stress corrosion to occur presence of stress and specific corrosive environment are must. Stressed areas of certain alloys become so chemically active that they are attacked, even by a mild corrosive environment, resulting in the formation of a crack, which grows and propagates in a direction perpendicular to operating stress. For example, () Season cracking (Stress Corrosion of Brass). Generally, it takes place in atmosphere containing NH, or RNH;. Both the alloying components of brass 2 Cu and Zn are known to form complex ions like [Cu (NHs)4]** and [Zn (NH),]*° in ammonia solutions. This leads to dissolution of brass which ultimately results in the formation of cracks in the presence of stress. (ii) Caustic embrittlement. Caustic embrittlement is the phenomenon durin which the boiler material becomes brittle due to the accumulation of causti substances. This type of boiler corrosion is caused by the use of highly alkaline water in the high pressure boiler. During softening by lime-soda process, it is likely that some residual Na,CO, is still present in the softened water. In high pressure boilers Na,CO, decomposes to give sodium hydroxide and CO, and sodium hydroxide thus produced makes the boiler water “caustic” Na,CO, + H,O —— 2NaOH+Co, This caustic water flows into the minute hair-cracks of boiler, by capillary action. On evaporation of water the disc g the inner side concentration increases progressively which attacks the surround pec caustic sods dissolving iron of boiler as sodium ferrate. This causes embrene a7e2. thereby walls more particularly stressed parts (like bends, joints, rive te™eNt Of boiler failure of the boiler. S, etc.), causing even6 PROTECTIVE MEASURES AGAINST CORROSION The methods used to protect a metal from corrosion mainly operate by pre- venting corrosion reactions from taking place. One of the best ways of doing this is to protect the metal from water and oxygen. The various protective measures include modification of the environment ; modification of the properties of the metal ; use of protective coatings and cathodic protection. Before protecting measures are adopted, the metal should be cleaned or ‘descaled’ by degreasing and descaling. Oily and greasy surface films are dissolved out by exposure to trichloroethy!- H a cl cl ene] C=C |, tetrachloroethylene| C=C ¢_| and other volatile a cl cl cl weeny organic solvents. Mechanical or chemical methods can be used for Descaling. The various protective measures are summarized below : 6.1 Modification of the Environment In this category, the metals are protected from corrosion either by remov: corrosion stimulants or by the use of inhibitors (ie, the substances which effec- tively decrease the corrosion rate). These are briefly discussed below : (a) Removal of corrosion stimulants. * To prevent corrosion due to the oxygen, dissolved oxygen from water is removed by physical or chemical means. Either Deaeration is done or reducing substances are added like N,H, Na,SO, etc To prevent corrosion by acids, they are neutralized with lime. To prevent corrosion by salts, they are removed by using ion-exchange resins, To prevent corrosion by moisture, moisture from air is removed by dehumidification using silica gel.CORROSION AND ITS CONTROL aime (b) Use of corrosion inhibitors. Inhibitors are inorganic or organic substances which when added to the environment are able to reduce the rate of corrosion6.1.2 Corrosion Inhibitor Inhibitors are chemical substances which reduce the corrosion rate when added in small quantities to the corrosive environment. Corrosion inhibitors are of following three types : (a) Anodic inhibitors like alkalis, molybdates, phosphates, chromates, etc They react with the ions of the anode and produce insoluble precipitates. The precipitates so formed are adsorbed on the metal surface, forming a protective film or barrier, thereby reducing the corrosion rate. (b) Cathodic inhibitors. In an acidic solution, the cathodic reaction is 2 H* + 2e” > H,, the corrosion can be controlled by slowing down the diffu- sion of H* ions through the cathode. It can be done by using organic inhibitors likeCORROSION AND ITS CONTROL em amines, mercaptans, heavy metal soaps, substituted ureas and thioureas. They absorb over the cathodic metal surface and act as a protective layer. Antimony and arsenic oxides deposit adherent film of metallic antimony or arsenic at the cathodic areas, thervby increasing considerably the overvoltage for hydrogen evolution In a neutral solution, the cathodic reaction is H,0+}.0,+26 20H" The formation of OH” ions is only due to the presence of oxygen. Therefore, corrosion can be controlled either by eliminating O, from the corroding medium (by adding reducing agents like Nay SO; or by deaeration) or by retarding diffusion of O, to the cathodic areas. It can be done by adding Zn, Ni or Mg salts which react with OH” at cathode to form insoluble hydroxides which are deposited on the cathode These deposits are impermeable barriers hence retard diffusion of O, to cathode. (©) Vapour Phase inhibitors are organic inhibitors which readily sublime and form a protective layer on the surface of metal. eg., dicyclohexylammonium nitrite is used for the protection of machineries and sophisticated equipments. Example 1. Why are the anodic inhibitors not considered to be satisfactory ? Solution. This is because, for each inhibitor, there is a certain critical concen- tration of solution above which inhibition may be expected. When an insufficient concentration is used, all the anodic areas may not be covered. The resulting combination (small anodic and large cathodic areas) leads to considerable increase in the current density (current flowing per unit area of the surface) at the few anodic sites. This causes rapid localized perforation of the metal (pitting). For cathodically controlled reactions, anodic inhibitors are especially dangerous, unless used in excess of the critical concentration. Example 2. (i) What are Organic inhibitors ? (ii) Give reasons. (a) The inhibiting power of aliphatic amines increases as NH3 < RNH3 < R2NH < R3N. where R is an alkyl group. (b) Inhibitors containing $ are usually more effective than N compounds. Solution. (i) Organic Inhibitors are S - or N - containing Organic compounds which retard corrosion processes even in acid solutions by getting adsorbed all over the metal surface. Examples : Amines, organic nitrites, Substituted thiocarbamides and hetrocyc- lic compounds. (ii) (a) This is because adsorption of amines increases with the basic strength of the N atom i.e, with the greater availability of the lone pair of electrons on the N atom. (b) Thisis because S (being less electronegative) is a better electron donor.A TEXT BOOK OF ENGINEERING CHEMISTRY 8.22 Example 3. Enlist one or tivo applications where volatile ier are used Solution. Volatile inhibitors [vapour-phase inhibitors ve enolate sono: sion inhibitors (VCI)] like dicyclohexy! ammonium nitrite (DC ) are used for protection against corrosion of metallic parts in small clare coma er i as machine parts packed and sent by ship). These are also used in compressors and condensers. 6.2 Modification of the Properti The properties of the metal can be modified to decrease the effects of corrosion The following methods are used to modify the properties of metals ies of the Metal 6.2.1 Alloying ‘The alloying additions for increasing corrosion resistance May be for Passivating. Al, Cr, Ti, Ni and Mo ; as protective oxide layers make steel less corrosive. Inhibiting. As or Sb in brass prevents dezincification. Neutralizing. Ta, Nb and Ti combine with carbon to form respective carbides and thus make the stainless steel, corrosion resistant. Mn and Cu combine with S in steels. Provided the [oxygen] is low, alloy containing much Ni, like mone! metal (Ni = 67%, Cu = 30%, Mn = Fe = 1.2% rest C and Si) have good corrosion resistance in acid solution. 6.2.2 Refining It is done to lower the content of $ and P in steels and C in stainless steels. 6.2.3. Annealing It is a heat treatment given to metals to remove the residual stresses. 6.3 _ Use of Protective Coatings For protection against corrosion, the metal surface may be coated with metal lic or non-metallic coatings. 63.1 Metallic Coatings Iron and steel are the most commonly used construction metals due to thei? low cost, easy availability and ease of fabrication into desired structures. lron and steel can be protected from corrosion by covering their surface with metalli coatings Surface coatings made up of metals are known as metallic coatings pasta coatings lias pads of zinc, tin, nickel, chromium, aluminium, coppe* These 1g8 separate the base metal from the corrosive environment and also function as an effective barrier for the protection of base metal: Types of Metallic coatings E There are two types of metallic coatings @ anet cosets 2 ame coatings, the metal which is used for coating 1S more “an Gel ors al which is to be protected (i.e., the base metal). Anodic coatings protect ying base metal sacnificially, For example, Coating of Al, Cd and Zn on steel surface. Let us discuss, ho™ galoanised steels protected from corrosion. Here Zn is coating metal and stee! isCORROSION AND ITS CONTROL. CS.23 base metal. Zn being anodic is attacked; leaving the underlying cathodic (iron/steel) unattacked, even if it is exposed when pores, breaks or discontinuities occur in such an anodic coating. Iron or steel is not corroded, till all the coating metal (Zn) is consumed. % Unexposed. YX WO electrons SN Geel SRN Fig. 10. Functioning of anodic coating. In galvanized steel, Zn serves an anode ; while iron of steel serves as the cathode. Therefore, the iron is protected, even ifitis exposed. (i) Cathodic coatings. These coatings protect the underlying base metal, due to their noble character and higher corrosion resistance. In such coatings, effective protection is possible only when they are completely continuous and free from pores, breaks or discontinuities. If pores, breaks or discontinuities occur in such a coating, the corrosion of the base metal is speeded up. This is due to the fact that exposed metal acts as anode and coating becomes the cathode. A galvanic cell is set up and an intense localized attack at the small exposed part occurs. This results in severe pitting and perforation of the base metal. Coating of tin on iron is an example. “orrosive environment = Exposed iron part = becomes anode ard is \Unexposed \» . Corrosion WS product electrons SSS (cathode) part OOo Sstee SS Fig. 11. Tin-plated steel. The tin protects the iron, when the coating is uniform. When the coating is broken, the iron of the steel becomes the anode ‘and is subjected to intense local corrosion. 6.3.2 Inorganic Coatings The inorganic coatings are non-metallic protective coatings. Important inor- ganic coatings are : (@ Surface conversion or chemical Dip coatings, (ii) Anodised oxide coating, (iii) Vitreous or Porcelain enamel coating. ) \saa A TEXT BOOK OF ENGINEERING CHEMISTRY These are briefly discussed below : (i) Surface conversion or chemical Dip coatings. The surface conversion is done for passivising the surface. This can be done by chemical or electrochemical reactions brought at the surface of the base metal. The resultant adherent coating on the surface of base metal gives good protection from corrosion. Such coatings are also used as an excellent base for the application of paints and enamels. Important surface conversion coatings are : (a) Phosphate coatings. These coatings are produced by the reaction of the base metal with an aqueous solution of phosphoric acid and phosphates of zinc, iron or manganese. This reaction is slow and can be accelerated by adding copper nitrate The copper nitrate acts as accelerator for the formation of phosphate coating. The resultant surface film consists of crystalline zinc-iron or manganese-iron phos- phates. , Phosphate coatings are applied frequently to iron, steel and zinc, and to small extent to aluminium, cadmium and tin. Such coatings do not offer complete resistance to atmospheric corrosion. Iron and manganese phosphate coatings are used to reduce wear due to friction in piston rings, cylinder lining of automobiles and wire drawing equipment. Phosphate coatings are principally used as an adher- ent base/ primer-coat for paint, lacquers, oils etc. Phosphate coating is usually grey in colour. The colour may bé modified to black by adding zinc sulphide (bonderiz- ing) to the bath, if it is not intended to paint, etc., the phosphate coated parts afterwards. (¥) Chromate coatings. Chromate coatings are obtained by the immeision of the metal in a bath having sodium dichromate and dilute sulphuric acid. At some critical pH, basic chromium chromate (Cr,O, . CrO; . x H,O) gets precipitated on the metal surface. Chromate coatings are non-porous, amorphous, and more corrosion-resistant than phosphate coatings. Chromate coatings are specially used for the protection of Mg, Al and Zn surfaces. Sometimes, they are also used as base for paints, lacquers and enamels. (c) Chemical oxide coatings. These coatings are provided on the surface of the base metal by treating them with alkaline oxidizing agent or gas. This treatment increases the thickness of the original oxide film on the metal, thereby increasing its corrosion-resistance. A good corrosion resistant black oxide coating on stainless steel is made by immersing steel in conc. NaOH. solution containing oxidising agents like sodium nitrite or sodium chlorate at 80 ~ 90°C Oxide coatings possess little absorptive power compared with that of phos- phate coatings, but they form a good base for paints, lacquers and oils. (ii) Anodised oxide coatings. These coatings are made by anodic oxidation rocess. This leads to the formation of protective, corrosion resistant, electrically Potting oxide film on the surface of non-ferrous metals like aluminium, zinc inst eta and their alloys n or anodising is an electrolytic process of oxidation for | oxide film on the surface of metal (like aluminium) to magnesi ‘Anodic oxidatior ing the natural thicken’ on against corrosion and mechanical injury. otection agi achieve more P*CORROSION AND ITS CONTROL cs.25 Anodising on aluminium is done by electrolysis in a suitable acid electrolyte (sulphuric, chromic, oxalic or phosphoric acid) at 35 to 40°C and moderate current densities. Aluminium is made the anode and a plate of lead or stainless steel is made the cathode. When the current is passed, the oxygen liberated at the anode combines with it to form the oxide, thus thickening the natural oxide film. The outer part of the oxide film formed is very porous and considerably softer than the layer directly adjoining the metal surface. The anodised surface is made impermeable by treatment with hot water. This treatment converts aluminium oxide into its mono- hydrate (Al,O, . H,O) which occupies more volume, thereby the pores are sealed. This sealing can also be done via. an alternative method which consists of immer- sion of the film in boiling dilute sodium dichromate solution. Anodized coatings on Zn can be obtained by making Zn as anode in an electrolytic bath containing chromic acid solution or chromates. These anodized coatings may be coloured with organic dyes and inorganic pigments to give decorative effects. When these coloured coatings are required, anodising is done at higher temperatures and in higher acid concentrations so as to. produce a porous coating and then immersing the article in a dye solution or precipitating an inorganic pigment in the film before the “sealing” operation.6.4 Cathodic Protection (or Electrochemical Protection) Let us consider the corrosion of a metal (M) in an acidic environment. Metal (M) undergoes corrosion by its oxidation (i.e., when metal behaves like an anode), This reaction is simultaneously accompanied by a reduction reaction viz., evolution of hydrogen gas M —— M"*+ne 2H'+2e ——>4 H, As is clear from the above reactions, we can prevent the dissolution of metal (its corrosion) by forcing the metal to behave like a cathode. This is the principle of cathodic protection. Since there will not be any anodic area on the metal, corrosion does not occur. Types of Cathodic Protection There are following two types of cathodic protection : (i) Sacrificial anodic protection. The metal structure can be saved from corro- sion by connecting it with wire to a more active (i.e., more anodic) metal, so that all the corrosion is concentrated at the more active metal. As the more active metal is sacrificed in the process of saving metal from corrosion, hence it is known as sacrificial anode. Metals commonly used as sacrificial anodes are Zn, Al, Mg and their alloys. Zinc is used as sacrificial anode in good electrolytes such as sea water. Magnesium is used in high resistivity electrolytes such as soils due to its most negative potential and it can provide highest current output. Applications. Important applications of this technique are : (a) Protection of underground cables and pipelines from soil corrosion {Fig. 12(@)]. (6) Protection of ships and boat hulls from marine corrosion. Sheets of Mg or Zn are hung around the ship hull, these sheets being anodic to iron so these sheets get corroded. When consumed completely, these are replaced by fresh ones [Fig. 12(b)]. (0) The formation of rusty water is prevented by the insertion of Mg sheets or rods into domestic water boilers or tanks [Fig. 12(c)]-Earth surface Sacrificial zine — or magnesium Mg (sacrifical anode) — Insulated copper wire 5 insulated copper wire Ship hull Insulated wire Sacrificial Znor Mg Fig. 12. Sacrificial anodic protection. (ii) Impressed current cathodic protection. In this method, current from an external source is impressed (applied in the opposite direction) to nullify the corrosion current. This is done to convert corroding metal from anode to cathode. Once the metal becomes cathodic, it is protected from corrosion. The anode may be either an inert material or one which deteriorates and will have to be replaced periodically. The commonly used anodic materials are graphite, carbon, stainless steel, scrap iron, high silica iron and platinum. The anode is buried in back fill such as gypsum to increase the electrical contact between itself and the surrounding soil. Source of impressed direct current Anode } Cathode Earth surface Graphite nsulatest Back fill ~e copper wire Buried pipe made cathode (protected) Fig. 13, Impressed current cathodic protection.CORROSION AND ITs CONTROL css Applications. This protection method is useful when electrolyte resistivity and current requirements are high. It is well-suited for large structures and long-term applications. Maintenance and Operating costs can be reduced by employing auto- matic impressed current cathodic protection. This protection technique is employed in the case of buried structures such as Pipe-lines, tanks, marine piers, transmission line towers, laid-up ships etc