UNIT II

Corrosion and its corrosion control

UNIT II: Corrosion and its corrosion control: Introduction, causes and different types of corrosion and effects of corrosion, Theories of corrosion - Chemical, Electrochemical corrosion, corrosion reactions, factors affecting corrosion - Nature of metal - galvanic series, purity of metal, nature of oxide film, nature of corrosion product. Nature of environment-effect of temperature, effect of pH, Humidity, effect of oxidant. Corrosion control methods - Cathodic protection, sacrificial anode, impressed current cathode. Surface coatings - methods of application on metals- hot dipping, galvanizing, tinning, cladding, electroplating Organic surface coatings - paints constituents and functions.

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Corrosion and its corrosion control

Corrosion and its corrosion control Introduction: The destruction and consequent loss of a solid metallic material, through an unwanted chemical or electrochemical attack by its environment, starting at its surface, is called corrosion. Corrosion can be a fast (or) slow process depending upon the metal, and environment in which it is undergoing corrosion. The familiar examples of corrosion: Rusting of Iron: A reddish brown scale formation on iron and steel objects. It is due to formation of hydrated ferric oxide. Green scales are formed on copper vessel. It is due to the formation of basic cupric carbonate(CuCO3+Cu(OH)2)

Causes: Most metals, except the nobel metals (Au, Pt etc), occur in nature in the form of their compounds such as oxides,sulphides,carbonates etc.The metals are extracted from ores in endothermic process, energy being supplied in the form of heat (or) electrical energy. Corrosion of metals occurs either by direct chemical attack (or) by electro chemical attack on the metal by corrosive environment. Direct chemical attack takes place generally in the absence of moisture. This type of corrosion is known as dry corrosion in which the constituents of the corrosion medium directly combine with metal due to their chemical affinity to the metal. Most of the corrosion cases are electrochemical in nature, taking place by the electrochemical attack on the metal in presence of moisture (or) conducting medium. Such corrosion is wet corrosion. Direct chemical or dry corrosion: According to this theory, direct chemical corrosion occurs due to the direct chemical reaction between the metal and the gases (oxygen, halogens, oxides of sulphur, and oxides of nitrogen, hydrogen sulphide and fumes of chemicals) present in the corrosion environment. This type of corrosion is generally observed in absence of moisture or conducting electrolyte medium, and therefore, known as Dry corrosion. Direct oxidation of metals and alloys on exposure to oxygen in air a common example of chemical corrosion. Two major factors deciding the rate of corrosion are the chemical affinity between the metal and the gases, and nature of the corrosion product formed. When oxidation starts, a thin layer of oxide is formed on the metal surface and the nature of this film decides the further action. (Stable, Unstable, Volatile, Porous) Pilling-Bedworth rule: The protective and non-protective nature of the oxide layer can be predicted on the basis of Pilling-Bed worth rule According to this rule an oxide is protective (or) non-porous, if the volume of the oxide is at least as great as the volume of the metal from which it is formed, and the oxide layer is porous (or) non-protective, if the volume of the oxide is less than the volume of metal from which it is formed. For example: Heavy metals such as Aluminium, chromium, lead, Tin, etc form an oxide film. Metals like alkali and alkaline earth metals form a porous oxide films, which allow further diffusion of oxygen to come in contact with fresh metal surface, thereby acts as a non-protective film. The extant of chemical corrosion by other gases such as CO2,SO2,Cl2,H2S,F2 etc also depends upon the formation of protective film (or) non-protective film by the corrosion product. Example: 1) The AgCl film from the attack of Chlorine on the silver metal surface is non-porous and protective. 2) SnCl4 formed on the surface of Tin by attack of chlorine is volatile, and leaves the fresh Tin surfaces for further attack.

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Corrosion and its corrosion control

Electro chemical theory of corrosion (or) Wet corrosion: Most of the corrosion problems are best explained on the basis of electro chemical corrosion. These are often called Wet corrosion since aqueous medium or moisture is required for corrosion to takes place. According to electro chemical theory, corrosion of metals takes place due to the formation of anodic and cathode regions on the same metal surface (or) when two different metals are in contact with each other in presence of a conducting medium. At anodic region oxidation reaction takes place and metal gets converted into its ions, liberation of electrons.Consequently, metal undergoes corrosion at anodic region. At Cathodic region, reduction reaction takesplace.Since the metal cannot be reduced further, metal atoms at the Cathodic regions are unaffected by the corrosion reactions. Some constituents of the corrosion medium take part in the cathodic reaction. The electrons liberated at anodic region migrate to cathodic region constituting corrosion current .The metal ions liberated at the anode and same anions formed at the cathode diffuse towards each other through the conducting medium and form a corrosion product. Somewhere between the anode and cathode. Corrosion of metals continues as long as both anodic and cathodic reactions take place simultaneously. There cannot be anodic reaction without cathodic reaction vice versa. To understand the wet theory, let us take the example of corrosion of iron. Oxidation of metal takes place at anode while the reduction process takes place at cathode. By taking rusting of iron as an example, the reaction can be explained as that it may occur in two ways: (i) evolution of hydrogen and (ii) absorption of oxygen

At anode: oxidation occurs. At cathode: Case I: Evolution of H2 The hydrogen ions (H+) are formed due to the acidic environment and the following reaction occurs in the absence of oxygen

2H+ + 2e-

The overall reaction is Fe + 2H+ Fe+2 + H2

H2

(reduction)

In this case, metals react in the acidic environment and are dissolved (undergo corrosion) to release H2 gas. All metals above hydrogen in electrochemical series can show this type of corrosion. In hydrogen evolution type of

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corrosion, anodic area is large as compared to its cathodic area Fig.b

Corrosion and its corrosion control

Case II: Absorption of O2 This type of corrosion takes place in neutral or basic medium in the presence of oxygen. The oxide of iron covers the surface of the iron. The small scratch on the surface creates small anodic area and rest of the surface acts as cathodic area. The following chemical reactions occur at anode and cathode.

At anode

Fe Fe++ + 2e

(oxidation)

Ferric hydroxide is actually hydrated ferric oxide, Fe2O3.H2O, which is yellowish rust. Anhydrous magnetite, Fe3O4 [a mixture of (FeO + Fe2O3)], is also formed, which is brown-black in colour. It is mark able that the corrosion occurs at anode but the corrosion product is formed near cathode. It is because of the rapid diffusion of Fe++ as compared to -OH (Fig. a). Hence corrosion occurs at anode, but rust is deposited at or near cathode.

S.No 1 2 3 4 5

Wet corrosion Corrosion occurs in presence of conducting Corrosion occurs in the absence of moisture medium It involves direct attack of chemicals on It involves formation of electrochemical cells the metal surface The process is slow It is a rapid process Corrosion products are produced at the Corrosion occurs at anode but rust is deposited site of corrosion at cathode It depends on the size of the anodic part of The process of corrosion is uniform metal
(b) Pitting Corrosion (c) Stress Corrosion (f) Soil Corrosion (h) Water-line Corrosion (j) Intergranular corrosion

Dry Corrosion

Types of corrosion: (a) Galvanic Corrosion (d) Crevice Corrosion (e) Erosion Corrosion (g) Micro-biological Corrosion (i) Differential aeration Corrosion

Galvanic Corrosion: This type of electrochemical corrosion is also called bimetallic corrosion. When two dissimilar metals are connected and exposed to an electrolyte, they will form a galvanic cell. The anodic metal will be oxidised and it will undergo corrosion. Zinc and copper metals connected with each other in an electrolyte medium form a galvanic cell. Zinc acts as anode and undergoes corrosion while cathode will be unaffected

At anode: At cathode:

Zn Cu
++

Zn++ + 2e- [Oxidation] corrosion

+ 2e- Cu [Reduction] unaffected

1. Galvanic corrosion can be avoided by coupling metals close to the electrochemical series. 2. Fixing insulating material between two metals. 3. By using larger anodic metal and smaller cathodic metal.

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Corrosion and its corrosion control

Example of galvanic corrosion: 1. Steel screws in brass marine hardware, 2. steel pipe connected to copper plumbing, 3. steel propeller shaft in bronze bearing, 4. zinc coating on mild steel, 5. lead-tin solder around copper wires. Pitting corrosion: Due to crack on the surface of a metal, local straining of metal, sliding under load, chemical attack, there is formation of a local galvanic cell. The crack portion acts as anode and rest of the metal surface acts as cathode. It is the anodic area which will be corroded and the formation of a pit is observed. This type of corrosion is thus called pitting corrosion. Metals owing to their corrosion resistance to their passive state show pitting and ultimately result in formation of passivity. Presence of external impurities such as sand, dust, scale embedded on the surface of metals lead to pitting. For example, stainless steel and aluminium show pitting in chloride solution.

At anode: Fe Fe 2++ 2e- [Oxidation] corrosion At cathode: O2+H2O +2e- 2 OH- [Reduction] unaffected Stress corrosion: In a metallic structure, if there is a portion under stress, it will act as anode and rest part of the structure will act as cathode. It is now a galvanic system and hence anodic part which is small in area will corrode more. Stress corrosions are observed in the following systems: Crevice corrosion: If surface of painted metal is scratched, it will undergo corrosion. The scratched portion acts as small anode and the rest part will act as cathode forming a local cell. Crevice corrosion is formed near joints, rivets and bolts. Changes in the concentration of oxygen/acidic medium causes crevice corrosion.

Crevice corrosion water line corrosion Waterline corrosion: It has been observed in the case of an iron tank containing water, that the portion of iron tank just below the water level undergoes corrosion. It is due to the difference in oxygen concentration. Corroding portion is poor in oxygen and acts as anode Example: When marine plants attach themselves to ocean going ships, water line corrosion is often accelerated and for its checking, use of anti-fouling paints is must. Inter-granular corrosion: This corrosion is observed in case of alloys. The corrosion product is observed at the boundaries of grains. Externally, it is not seen. There is a sudden failure of material due to this Corrosion. For example, during the welding of stainless steel (an alloy of Fe, C, Cr), chromium carbide is precipitated at the grain boundaries and the region adjacent to grain boundaries becomes depleted of chromium composition and is made anodic with respect to solid solution within the grains richer in chromium. Rapid quenching after heat treatment of a metal is the remedy of inter-granular corrosion

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Corrosion and its corrosion control

Factors affecting corrosion: There are several factors which influence the rate of corrosion to a varying degree. Some of the important factors affecting the rate of corrosion are discussed below. 1.Nature of the metal: The tendency of a metal to undergo corrosion is dependent on the nature of the metal. In general, the metals with low electrode potential values are more reactive than the metal with high electrode potential values. The more reactive metals are more susceptible for corrosion. Thus the tendency of a metal to undergo corrosion decrease with increase in electrode potential. For example: The so called metals like K,Na,Mg,Zn etc with low electrode potential values are highly susceptible for corrosion. The noble metals such as Ag, Gold, and Pt with high electrode potential values are less susceptible for corrosion. Galvanic series: Galvanic series have been prepared which gives real and useful information regarding the corrosion behaviour of meals and alloys in a given environment.

GALVANIC SERIES 2. Hydrogen over voltage: A metal with low hydrogen over voltage on its surface is more susceptible for corrosion, when the cathodic reaction is hydrogen evolution type. With lower hydrogen voltage, hydrogen gas is liberated easily and thus the cathodic reaction is faster. This will make the anodic reaction also faster, thereby promoting overall corrosion reaction. When the hydrogen over voltage on the metal surface is high, cahtodic reaction is slower and the corrosion of the metal also becomes slower. 3. Purity of metal: Impurity in metals causes heterogeneity and hence small localized galvanic cells and therefore enhancement of corrosion.

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Corrosion and its corrosion control

Example: If Zn metal is contaminated with impurities like Pb or Sn which are at higher level than Zn they use Zn as sacrificial anodes and hence more corrosion is seen in comparison to pure metal. 4. Nature of oxide film: The smaller the specific volume ratio [vol of metal oxide/vol of metal] greater is the oxidation corrosion, because oxide film formed will porous, through which oxygen can diffuse and bring above further corrosion. Example: The specific volume ratios of W, Cr, and Ni are 3.6, 2.6, and 1.6 respectively.Consequently; the rate of corrosion W is least, even at high temperatures. 5. Nature of corrosion product: If the corrosion product deposited in insoluble, stable, uniform and porous, it acts as a protective film, preventing the further corrosion of metal. A thin, invisible, continuous film formed on the surface acts as barrier between the fresh metal surface and the corrosion environment. The fresh metal surface and the corrosion product is soluble, unstable, on-uniform and porous, the corrosion continuous unabated. In such cases the fresh metal surface is continuously exposed to the corrosion environment and corrosion of the metal surface takes place continuously. 6. Nature of environment: Effect of temperature: The rate of a chemical reaction, in general increases with rise in temperature. Corrosion process (redox reaction) is one such chemical reaction.Therefore, the rate of corrosion increase in temperature increase the conductance of the corrosion medium, which also contributes to the increase in corrosion rate. Effect of p H: In general, lower pH of the corrosion medium, higher is the corrosion medium.However; some metals like Al, Zn e.t.c undergo fast corrosion in highly alkaline solution. The pH of the solutions also decides the type of cathodic reaction. Humidity: The greater is humidity, the greater is the rate and extent of corrosion. This is due to the fact that moisture acts as solvent for O2,H2S,SO2, and NaCl etc to furnish the electrolyte essential for setting up a corrosion cell.Example:1.Atmosphere corrosion of iron is slow in dry air compared to moist air.2.Gases like H2S,SO2 etc increases the acidity of medium by their dissolution in water and hence increases the corrosion rate.3.Dissulution of NaCl in water leads to increased conductivity and thereby increased corrosion rate. Effect of oxidant: The presence of oxidizing agents increase the corrosion rate of the metal. Systems handling water like boilers, heat exchangers etc are faced with serious corrosion problem permissible. Even Nobel metals undergo corrosion in presence of oxidizing agents.

S.NO

GALVANIC SERIES

ELECTROCHEMICAL SERIES

1 2 3 4 5

It predicts the corrosive tendencies of metal alloys Calomel electrode is used as a reference electrode Positioning of metal or alloy may change

It predicts the relative displacement tendencies Standard hydrogen electrode is used as reference electrode

Position of metal is fixed. That cannot be changed The metals and alloys are immersed in the concentration of salts of the same metal that sea water for study was being used Electrode potentials are measured for both Electrode potentials measured only for metals and alloys metals and non-metals

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Corrosion and its corrosion control

Corrosion control:Cathodic protection: - Cathodic protection is a method of protecting a metal (or) alloy from corrosion by converting it completely in to cathodic and of it is allowed to act as anode. Principle:-Metals normally undergo corrosion by electrochemical process with the formation of anodic and cathodic regions in contact with each other. The corrosion of metal takes place at the anodic region whereas at the cathodic the metal is unaffected.Therefore, corrosion can be prevented by eliminating the anode sites and converting the entire metal into cathodic area. Cathodic protection can be achieved by the following methods *Sacrificial anode method *Impressed current method Sacrificial anode method:-In this method, the protected metal surface is converted into a cathode by connecting it to a more active metal. This active metal acts as an auxiliary anode.Zn, Mg, Al, are the common auxiliary anodes used in this method. These metals, being more active, acts as anode and undergo preferential corrosion, protecting in the metal structure. Since the anodic metals are sacrificed to protect the metal structure, the method is known as Sacrificial anode method. Examples: 1) A Mg block connected to a buried oil storage tank. 2) Mg blocks are connected to bury pipe lines.

SACRIFICIAL ANODE METHOD

IMPRESSED CURRENT METHOD

Impressed current method:-Another method of providing cathodic protection is by applying a direct current larger than the corrosion. The protected metal is made Cathodic by connecting it to cathode of external source of current .The anode of the source is connected to an inert electrode. The metal structure being cathode does not undergo corrosion. Anode being inert remains unaffected. Graphite is widely used as inert anode in this method. Platinum, Silicon, Iron also used as anodes. Advantages:1) One installation can protect large of metals 2) Low maintains cost. Surface coatings methods of applications on metals: The following are the methods of applications of the metallic coatings. Hot dipping: This is a method of coating a low melting metal such as Zn,Sn,Pb,Al etc on iron ,steel and copper which have relatively higher melting points. The base metal is dipped in the molten bath of the coating metal,
which covered by a molten flux layer which cleans the base metal surface and prevents the oxidation of coating metal. For adhesion of the coating metal on the surface of the base metal, the base metal surface must be very clean. The most widely used hot dipping methods are (a) Galvanisation (b) Tinning

Galvanisation: It is a process of coating iron or steel sheets with a thin coat of Zinc to prevent iron from rusting. The base metal iron or steel is cleaned by acid pickling method with dilH2SO4 for 15-20 min at 60-900 C.The sheet is then washed well and dried .It is dipped in a bath of molten Zinc maintained at 425-4300C .The surface of the bath is kept covered with ammonium chloride flux to prevent oxide formation. The sheet is taken out and excess of Zinc is removed by passing it between a pair of rollers. Then the sheet is subjected to annealing process at 6500C and cooled slowly. An alloy of iron and zinc were formed at the junction of the base metal and coating metal.

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Corrosion and its corrosion control

Applications: It is mostly used to protect iron used for roofing sheets, wires, pipes, nails, bolts, screws, bucketsand tubes. Galvanised utensils cannot be used for preparing and storage food stuffs especially acidic in nature, because zinc dissolves to form highly toxic or poisonous compounds
N H 4C l flu x P a ir o f h o t ro lle r s

G a lv a n iz in g sheet

Hot a ir M o lte n Z in c a t 4 2 5 -4 3 0 0 C

Iro n sheet

D il.H 2 S O A t 6 0 -9 0

4 0

W a s h in g b a th

D ry in g cham ber

E xcess o f Z in c

A n n e a lin g cham ber

Galvanisation of steel sheet Tinning: Coating tin over iron or steel articles is called tinning. In this process the surface of the base metal (iron sheet) is cleaned by acid pickling with dil.H2S04 and passed through a bath of zinc chloride flux. The flux helps the molten tin bath and pressed between two rollers from a layer of palm oil. Palm oil helps to protect the tin coated against oxidation. The rollers remove excess of tin and produce a thin film of uniform concentration. An alloy of the base metal and coating metal at their junction is produced. Applications: 1.The metals possess good resistance atmospheric corrosion. Tin non toxic and widely used for coating steel, copper, and brass sheets.2.The containers coated with tin is used for storing food stuffs,Ghee,oils and packing food materials.
Rolers ZnCl 2 Flux Tin plated sheet Palm oil

Molten Tin

Tank

Acid pickling

Metal cladding: In this process a dense, homogenious layer of coating metal is bonded (cladded) firmly and permanently to the base metal on one or both sides .The metal cladded is cladded is called cladding metal. The choice of cladding metals depends on the corrosion resistance required for any particular environment. The corrosion resistance metals like Ni, Cu, Pb, Ag, Pt etc and alloys like stainless steel, Nickel alloys, copper alloys are used as cladding materials. The common base metals cladded are mile steel, aluminium, copper, nickel and their alloys. 99.5% pure aluminium is subjected to cladding to protect duraluminium to produce Alclad which is widely used in aircraft industry.

Applications: This method is widely adopted in aircraft industry and automobile industry. 9

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Corrosion and its corrosion control

Electroplating: The process of depositing the coating metal on the surface of the base metal/non metal by electrolysis is called electroplating. Applications: Electroplating is a most important and frequently used technique in industries to produce metallic coating. Both metals and non metals can be electroplated. In metals electroplating increases resistance to corrosion, chemical attack, hardness and hardness and surface properties. In non metals electroplating increase strength and decorates the surface of non metals like plastics, wood, glass etc.
Organic surface coatings It is an important established to protect a metal surface and other constructional materials from corrosion by using paints.Varnishes, enamels and lacquers. They are collectively come under the category of organic coatings. Two important functions of organic coatings To impart decorative and aesthetic appeal and To protect the metal from corrosion Paints: Wood, metal, cement, bricks etc are well known as constructional materials for our homes, offices, industries etc.Over a period of time Metal surface gets scratched and warped Wooden surface gets scratched and warped Walls crack and chip Paints forms a protective layer over these surfaces and keep them looking as good as new. Essentially paint is a combination of following Pigments:-Which give a paint its colour and opacity Solvents:-Which give a paint its flow and enable it to be brushed on a surface Additives:-Which give a paint special properties like resistance to fungus ,rust etc Requirements of a good paint: It should be fluid enough to be spread on the metal surface easily It should have a high covering power It should form a quite tough,uniform,adherent,and impervious film The film should not crack on drying It should give glossy film It should adhere well to surface Constituents of paints and their functions: The important constituents of paint are
P a in t

P ig m e n ts

V e h ic le s T h in n e r s

D r ie r s F ille r s

P la s tic is e r s A n ti- S k in n in g a g e n ts

Pigments: - Pigment is a one of the essential constituent of paint Functions: To give aesthetical appeal to the paint film To provide desired colour, opacity and strength to paint To give protection to the paint film by reflecting harmful UV light To improve impermeability of paint film to moisture. Characteristics of good pigments: Chemically inert Non toxic Easily available

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Corrosion and its corrosion control

Freely mixable with oil Cheap, it should also posses higher covering power Pigment types: Natural (Ex: Talc, clay), Synthetic (Ex: Titanium oxide, Barium sulphate), Reactive (Ex: Red lead and ZnO) Vehicle (or) drying oil: - It is a film forming constituent of the paint. The liquid portion of the paint in which the pigment is dispersed called medium (or) vehicle (or) drying oil Functions: They hold the pigment on the metal surface They form the protective film These give better adherence to the metal surface Thinners:-Viscosity of the paints is reduced by the addition of thinners. This is essential so that the paints can be easily applied on the metal surface. Example: Turpentine, Benzene, Kerosene Functions: They suspended the pigments in the paint They increase the elasticity of the paint film They evaporate rapidly and help in the drying of the paint film They also increase the penetration power of vehicles. Driers:-The drying of the oil film is accelerated (or) catalyzed by driers. They do this by oxidation, polymerisation, and condensation.Infact driers are oxygen-carrier catalysts Example: Borates, Naphthalene, Resinates. Functions: The main function of drier is to improve the drying quality of the oil-film. They acts as oxygenated carrier catalyst which help the absorption of oxygen and catalyze the drying of the oil film. Filler:-Fillers are inert materials which are used to improve the properties and reduce the cost of paint. Example: Talc, Chalk, Silica, Calcium carbonate, Calcium sulphate, Barium sulphate Functions: They reduce the cost of paint They serve to fill the voids in the film Plasticizer:-Plasticizers are added to the paint film to give elasticity to the paint film and to prevent cracking of the film. Example: Tricresyl phosphate, Dibutyl tartarate Anti-skinning agents:-Anti-skinning agents prevent the gelling and skinning of the paint film. Example: Poly hydroxyl phenols.

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