CORROSION CONTROL METHODS Some of the commonly used methods to control/prevent corrosion include: HUMIDITY Control the level

of humidity around the metal. For example, Water reacts with iron to form carbonic acid, which breaks down the bonds of the iron. At the same time, at least some of the water is broken up into hydrogen and oxygen. When iron comes in contact with the oxygen from the water, the oxygen and iron bond to form iron oxide (rust). By keeping the humidity level low around an object containing iron, the amount of corrosion that will occur is minimized. Dehumidifiers are a simple, inexpensive way to control the humidity in a confined environment. PURITY OF METAL Corrosion resistance of a metal increases on increasing its purity. This is because impurities help in creating tiny electrochemical cells and to promote corrosion due to heterogeneity. PROTECTIVE COATINGS Materials preferred as coatings should be chemically inert and must be capable of preventing the penetration of the environment to the base metal. It should also be wear-resistant, hard, oxidation resistant and thermally insulated. PAINTING Coat the surface of the metal with a corrosion-resistant paint. The paint will serve as a barrier between the metal and the moisture and other corrosive agents that can come in contact with it. With such a barrier in place, the chemical reactions that leads to the formation of oxides, sulphides, carbonates etc:- on the surface of the metal are deterred. But since paint wears away over time, the surface must be repainted regularly. OIL / GREASE / TAR / PLASTIC

Like paint, oil also acts as a protective barrier between the metal surface and corrosive agents. This method works best for small objects, such as iron tools, but it also can be used for small parts of larger structures, such as iron bolts. METALLIC COATINGS ANODIC COATING Base metal is protected sacrificially Electrode potential of the coating metal is lower than that of the base metal. The base metal will not undergo corrosion until all the coating metal is consumed even if some pores or breaks appear in such coating. Example; Coating of zinc on iron

CATHODIC COATING Here a noble metal of higher corrosion resistance protects the base metal. Electrode potential of the coating metal is higher than that of the base metal. The coating should be continuous. Any pores or breaks in the coating will speed up corrosion. Example; Coating of tin on iron.

PROPER DESIGNING Figs 3.10, 3.11, 3.12 CATHODIC PROTECTION In this method the metal to be protected from corrosion is made to act as a cathode. Its most commonly used to protect steel, water, and fuel pipelines and tanks. SACRIFICIAL ANODIC PROTECTION

This process involves the enclosement of a metal to be protected with a more reactive anodic metal which will corrode first, thus protecting the lower layer. The more active metal so used is called sacrificial anode. 'Rusting' can be prevented by connecting iron to a more reactive metal (e.g., zinc or magnesium). This is referred to as sacrificial protection or sacrificial corrosion, because the more reactive protecting metal is preferentially oxidized away, leaving the protected metal intact. (fig 3.13 from page 3.14) IMPRESSED CURRENT CATHODIC PROTECTION (ICCP) For larger structures galvanic anodes cant deliver current economically for complete protection. ICCP systems use anodes connected to DC power source. Anodes for ICCP systems are tubular and solid rod shapes of various specialized materials like graphite, mixed metal oxide etc:-. (3.14) ANODIC PROTECTION Anodic protection impresses anodic current on the structures to be protected (opposite to the cathodic protection). It is appropriate for those metals that exhibit passivity (stainless steel) and suitably small passive current over a wide range of potentials. It is used in aggressive environments eg:- solutions of sulphuric acids. ALTERING THE ENVIRONMENT It involves removal of the problem making constituents or by adding substances capable of nullifying the activity of the corrosive constituent. Different methods included are: Deaeration removal of dissolved oxygen by mechanical agitation. Deactivation Addition of chemicals which rapidly combine with the oxygen present in aqueous solution. Dehumidification reduce water content in air Alkaline neutralization acidic character of the corrosive environment neutralized using alkaline media. ALLOYING

Metals can also be protected by 'alloying' or mixing with other metals (e.g., chromium) to make non-rusting alloys. Alloys are homogenous solid solution of 2 or more metals. Corrosion resistance of most metals increases when it is alloyed with suitable elements. Stainless steel is an example of a non-rusting alloy of iron and carbon. Brass, an alloy containing copper is another metal alloy which is less expensive and non reactive. ADDITION OF CORROSION INHIBIORS Substances which when added in small quantities to the corroding solution, decrease the corrosion of the metal are called corrosion inhibitors. There are 2 types of inhibitors : Anodic inhibitors and cathodic inhibitors. PASSIVATION GALVANISING Coating iron or steel with a thin zinc layer is called 'galvanising'. This layer is produced by electrolytic deposition. Dipping the iron/steel object in molten zinc and using it as the negative cathode zinc is coated on it. Zinc preferentially corrodes or oxidizes to form a zinc oxide layer that does not flake off like iron oxide rust. This process resembles sacrificial protection. Also, if the surface is scratched, the exposed zinc again corrodes before the iron and continues to protect it. But this process is not good for the protection of cooking utensils because zinc dissolves in dilute acids to give highly poisonous compounds. TINNING This method consists of coating tin over iron or steel articles. Excellent corrosion resistance and non toxic nature of tin makes it a highly suitable material to coat containers made of steel, copper, etc. used for cooking and storing food stuffs. METAL CLADDING

This metal consists of bonding firmly and permanently a dense, homogeneous layer of coating metal on the base metal on one or both sides. Corrosion resistant metals like silver, copper, etc. and their alloys are general preferred. The base metal sheet is kept between two thin sheets of the coating metal and passed through rollers under high temperature and pressure. For example, alcad produced in this method is used in aircraft industry.

ELECTROPLATING It is the process by which metals are deposited on metallic surfaces by electrolysis. The surface is coated with metals like tin, chromium, nickel, gold, silver, etc. The method involves passing a direct current through a soluble salts solution of the plating metal; the object to be plated is made the cathode whereas the anode is either the coating metal itself or an inert material of good electrical coCORROSION CONTROL METHODS Some of the commonly used methods to control/prevent corrosion include: HUMIDITY Control the level of humidity around the metal. For example, Water reacts with iron to form carbonic acid, which breaks down the bonds of the iron. At the same time, at least some of the water is broken up into hydrogen and oxygen. When iron comes in contact with the oxygen from the water, the oxygen and iron bond to form iron oxide (rust). By keeping the humidity level low around an object containing iron, the amount of corrosion that will occur is minimized. Dehumidifiers are a simple, inexpensive way to control the humidity in a confined environment. PURITY OF METAL Corrosion resistance of a metal increases on increasing its purity. This is because impurities help in creating tiny electrochemical cells and to promote corrosion due to heterogeneity. PROTECTIVE COATINGS

Materials preferred as coatings should be chemically inert and must be capable of preventing the penetration of the environment to the base metal. It should also be wear-resistant, hard, oxidation resistant and thermally insulated. PAINTING Coat the surface of the metal with a corrosion-resistant paint. The paint will serve as a barrier between the metal and the moisture and other corrosive agents that can come in contact with it. With such a barrier in place, the chemical reactions that leads to the formation of oxides, sulphides, carbonates etc:- on the surface of the metal are deterred. But since paint wears away over time, the surface must be repainted regularly. OIL / GREASE / TAR / PLASTIC Like paint, oil also acts as a protective barrier between the metal surface and corrosive agents. This method works best for small objects, such as iron tools, but it also can be used for small parts of larger structures, such as iron bolts. METALLIC COATINGS ANODIC COATING Base metal is protected sacrificially Electrode potential of the coating metal is lower than that of the base metal. The base metal will not undergo corrosion until all the coating metal is consumed even if some pores or breaks appear in such coating. Example; Coating of zinc on iron

CATHODIC COATING Here a noble metal of higher corrosion resistance protects the base metal. Electrode potential of the coating metal is higher than that of the base metal.

The coating should be continuous. Any pores or breaks in the coating will speed up corrosion. Example; Coating of tin on iron.

PROPER DESIGNING Figs 3.10, 3.11, 3.12 CATHODIC PROTECTION In this method the metal to be protected from corrosion is made to act as a cathode. Its most commonly used to protect steel, water, and fuel pipelines and tanks. SACRIFICIAL ANODIC PROTECTION This process involves the enclosement of a metal to be protected with a more reactive anodic metal which will corrode first, thus protecting the lower layer. The more active metal so used is called sacrificial anode. 'Rusting' can be prevented by connecting iron to a more reactive metal (e.g., zinc or magnesium). This is referred to as sacrificial protection or sacrificial corrosion, because the more reactive protecting metal is preferentially oxidized away, leaving the protected metal intact. (fig 3.13 from page 3.14) IMPRESSED CURRENT CATHODIC PROTECTION (ICCP) For larger structures galvanic anodes cant deliver current economically for complete protection. ICCP systems use anodes connected to DC power source. Anodes for ICCP systems are tubular and solid rod shapes of various specialized materials like graphite, mixed metal oxide etc:-. (3.14) ANODIC PROTECTION Anodic protection impresses anodic current on the structures to be protected (opposite to the cathodic protection). It is appropriate for those metals that exhibit passivity (stainless steel) and suitably small passive

current over a wide range of potentials. It is used in aggressive environments eg:- solutions of sulphuric acids. ALTERING THE ENVIRONMENT It involves removal of the problem making constituents or by adding substances capable of nullifying the activity of the corrosive constituent. Different methods included are: Deaeration removal of dissolved oxygen by mechanical agitation. Deactivation Addition of chemicals which rapidly combine with the oxygen present in aqueous solution. Dehumidification reduce water content in air Alkaline neutralization acidic character of the corrosive environment neutralized using alkaline media. ALLOYING Metals can also be protected by 'alloying' or mixing with other metals (e.g., chromium) to make non-rusting alloys. Alloys are homogenous solid solution of 2 or more metals. Corrosion resistance of most metals increases when it is alloyed with suitable elements. Stainless steel is an example of a non-rusting alloy of iron and carbon. Brass, an alloy containing copper is another metal alloy which is less expensive and non reactive. ADDITION OF CORROSION INHIBIORS Substances which when added in small quantities to the corroding solution, decrease the corrosion of the metal are called corrosion inhibitors. There are 2 types of inhibitors : Anodic inhibitors and cathodic inhibitors. PASSIVATION GALVANISING Coating iron or steel with a thin zinc layer is called 'galvanising'. This layer is produced by electrolytic deposition. Dipping the iron/steel object in molten zinc and using it as the negative cathode zinc is coated on it. Zinc preferentially corrodes or oxidizes to form a zinc oxide layer that does not

flake off like iron oxide rust. This process resembles sacrificial protection. Also, if the surface is scratched, the exposed zinc again corrodes before the iron and continues to protect it. But this process is not good for the protection of cooking utensils because zinc dissolves in dilute acids to give highly poisonous compounds. TINNING This method consists of coating tin over iron or steel articles. Excellent corrosion resistance and non toxic nature of tin makes it a highly suitable material to coat containers made of steel, copper, etc. used for cooking and storing food stuffs. METAL CLADDING This metal consists of bonding firmly and permanently a dense, homogeneous layer of coating metal on the base metal on one or both sides. Corrosion resistant metals like silver, copper, etc. and their alloys are general preferred. The base metal sheet is kept between two thin sheets of the coating metal and passed through rollers under high temperature and pressure. For example, alcad produced in this method is used in aircraft industry.

ELECTROPLATING It is the process by which metals are deposited on metallic surfaces by electrolysis. The surface is coated with metals like tin, chromium, nickel, gold, silver, etc. The method involves passing a direct current through a soluble salts solution of the plating metal; the object to be plated is made the cathode whereas the anode is either the coating metal itself or an inert material of good electrical conductivnductivity.

CORROSION

Corrosion is the deterioration/disintegration of materials by chemical interaction with their environment. The term corrosion is sometimes also applied to the degradation of plastics, concrete and wood, but generally refers to metals. Corrosion of Metals can be described as the slow process of deterioration / destruction of the metal resulting in the loss of solid metallic material through unwanted chemical or electrochemical changes taking place at its surface. It is a chemical process by which the metal is oxidized. A well known example of an electrochemical corrosion is the rusting of iron, which involves the process of formation of an oxide of iron due to oxidation of the iron atoms in solid solution. The tendency to corrode in a given environment varies with the particular metal. Other common examples of corrosion include tarnishing of silver, copper etc:The international standard definition of corrosion is as follows: "Physicochemical interaction between a metal and its environment which results in changes in the properties of the metal and which may often lead to impairment of the function of the metal, the environment, or the technical system of which these form a part". (ISO 8044-1986) A broader, but widely accepted alternative definition, from the International Union of Pure and Applied Chemistry (IUPAC) encompasses the degradation of non-metals as well as metallic materials, as follows: "Corrosion is an irreversible interfacial reaction of a material (metal, ceramic, polymer) with its environment which results in consumption of the material or in dissolution into the material of a component of the environment. Often, but not necessarily, corrosion results in effects detrimental to the usage of the material considered. Exclusively physical or mechanical processes such as melting or evaporation, abrasion or mechanical fracture are not included in the term corrosion."

FACTORS INFLUENCING CORROSION

NATURE OF CORRODING ENVIRONMENT

a)

b)

Temperature: The rate of corrosion tends to increase with rising temperature. As temperature increases, rate of reaction, diffusion etc:- also increases. Temperature also has a secondary effect through its influence on the solubility of air (oxygen), which is the most common oxidizing substance influencing corrosion. Humidity: Rate of corrosion increases with increase in humidity in the atmosphere. This is because atmospheric gases like CO2, O2 etc:- have the tendency to dissolve in the moisture to form an electrolyte, giving rise to an electrochemical corrosion cell. The oxide film on the metal surface may also absorb moisture leading to corrosion. Critical humidity is the relative humidity above which the atmospheric corrosion rate increases sharply.

c)

Effect of pH: Generally an acidic media (pH<7) is found to be more corrosive than a basic (pH>7) or neutral media (pH=7). Therefore, corrosion due to attack of an acid can be minimized by increasing the pH of the system.

1. Acid-soluble metals such as iron have a relationship as shown in Fig. a below. In the middle pH range (4 to 10), the corrosion rate is controlled by the rate of transport of oxidizer to the metal surface. Iron is weakly amphoteric. At very high temperatures such as those

encountered in boilers, the corrosion rate increases with increasing basicity, as shown by the dashed line.

2. Amphoteric metals such as aluminum and zinc have a relationship as shown in Fig. b. These metals dissolve rapidly in either acidic or basic solutions.

3. Noble metals such as gold and platinum are not appreciably affected by pH, as shown in Fig. c.

d) Existence of corrosive impurities in atmosphere: Increase in the presence of corrosive gases like CO2, H2S, SO2 and fumes of HCl, H2SO4 etc:- can lead to an increased corrosion rate. As already mentioned, corrosion increases with decrease in pH. So increase in acidity of the liquid surrounding the metal leads to an increase in the electrical conductivity. e) Flow velocity: Flow velocity of process streams increases the diffusion and corrosion rates. Therefore to decrease the corrosion rate, in case of non-passivating type corroding metals, minimization of flow velocity helps. f) Formation of oxygen concentrating cell: Waterline corrosion, crevice corrosion etc:- are attributed to the formation of oxygen concentration cells. Oxygen concentration cell formed due to differential aeration promotes corrosion particularly at regions of low oxygen concentration. The less oxygenated part becomes anodic and the more oxygenated part becomes cathodic, thus setting up an oxygen conc. resulting in corrosion. g) Nature of surrounding ions: The ions surrounding the particular metal also has an influence on its corrosion pattern. There may be ions, which in the presence of that metal lead to an increased corrosion rate. Iron for example undergoes rapid corrosion in a medium of ammonium salts. But there are also ions in whose presence corrosion is prevented by formation of a protective coat on the metal. Silicate ions help in formation of silica gel on the metal surface, preventing further corrosion.

h) Conductance of corroding media: If the surrounding media is soil containing clay and minerals, the metallic structures buried inside them undergo severe damage due to corrosion than that buried under dry sandy soils because the former is more conducting. i) Polarisation of electrodes: Substances capable of dissolving in the corroding medium to develop a protective layer either at the anodic or cathodic area called corrosion inhibitors can make irreversible changes around the electrodes, opposing the direction of corrosion current flow. This polarisation of electrodes decreases the potential at both electrodes. Hence corrosion rate also decreases. (Figure 3.9 from page 3.11) Evans diagrams are obtained when potentials of polarized electrodes are plotted against current in the corrosion circuit.

TYPES OF CORROSION

It is convenient to classify corrosion by the forms in which it manifests itself, the basis for this classification being the appearance of the corroded metal. Some of the various forms of corrosion are quite unique, but all of them are more or less interrelated. The ten main forms of corrosion are: 1) Dry corrosion 2) Wet corrosion 3) Rusting of iron 4) Galvanic corrosion 5) Pitting corrosion 6) Intergranular corrosion 7) Water line corrosion 8) Stress corrosion 9) Concentration cell corrosion 10) Microbiological corrosion

Other forms of corrosion include uniform corrosion, crevice corrosion, graphitic corrosion, selective leaching, erosion corrosion etc:-

Uniform or General Corrosion: The reaction starts at the surface and proceeds uniformly. The metal loss is uniform from the surface. Its often combined with high-velocity fluid erosion, with or without abrasives.

Pitting Corrosion: The metal loss is randomly located on the metal surface. The basis metal is eaten away and perforated in places in the manner of holes, the rest of the surface being affected only slightly or not at all. Its often combined with stagnant fluid or in areas with low fluid velocity.

Galvanic Corrosion: Occurs when two metals with different electrode potential is connected in a corrosive electrolytic environment. Increased corrosion in crevices or cracks or at contact surfaces between two metal articles. The anodic metal develops deep pits and groves in the surface.

Crevice Corrosion: Occurs at places with gaskets, bolts and lap joints where crevice exists. Crevice corrosion creates pits similar to pitting corrosion. Graphitic Corrosion: Cast iron loosing iron in salt water or acids. Leaves the graphite in place, resulting in a soft weak metal. Wide pitting corrosion: The corrosion causes localized scarring.

Intergranular corrosion: Imperceptible or barely perceptible from outside, since the corrosion proceeds at the grain boundaries.

Transgranular or intragranular corrosion: The grain boundary material is retained, since the corrosion proceeds preferentially within the grain.

Selective corrosion: Corrosive attack on structural constituents

Exfoliation corrosion: Occurs in deformed articles. Corrosion follows "fiber orientation".

Interfacial corrosion: Frequently observed at water-air interfaces.

Galvanic or Two-Metal Corrosion A potential difference usually exists between two dissimilar metals when they are immersed in a corrosive or conductive solution. If these metals are placed in contact (or otherwise electrically connected), this potential difference produces electron flow between them. Corrosion of the less corrosion-resistant metal is usually increased and attack of the more resistant material is decreased, as compared with the behavior of these metals when they are not in contact. The less resistant metal becomes anodic and the more resistant metal cathodic. Usually the cathode or cathodic metal corrodes very little or not at all in this type of couple. Because of the electric currents and dissimilar metals involved, this form of corrosion is called galvanic, or two-metal, corrosion. Pitting Pitting is a form of extremely localized attack that results in holes in the metal. These holes may be small or large in diameter, but in most cases they are relatively small. Pits are sometimes isolated or so close together that they look like a rough surface. Generally a pit may be described as a cavity or hole with the surface diameter about the same as or less than the depth.

Pitting is one of the most destructive and insidious forms of corrosion. It causes equipment to fail because of perforation with only a small percent weight loss of the entire structure. It is often difficult to detect pits because of their small size and because the pits are often covered with corrosion products. In addition, it is difficult to measure quantitatively and compare the extent of pitting because of the varying depths and numbers of pits that may occur under identical conditions. Pitting is also difficult to predict by laboratory tests. Sometimes the pits require a long time-several months or a year-to show up in actual service. Pitting is particularly vicious because it is a localized and intense form of corrosion, and failures often occur with extreme suddenness. Intergranular Corrosion Grain boundary effects are of little or no consequence in most applications or uses of metals. If a metal corrodes, uniform attack results since grain boundaries are usually only slightly more reactive than the matrix. However, under certain conditions, grain interfaces are very reactive and intergranular corrosion results. Localized attack at and adjacent to grain boundaries, with relatively little corrosion of the grains, is intergranular corrosion. The alloy disintegrates (grains fall out) and/or loses its strength. Intergranular corrosion can be caused by impurities at the grain boundaries, enrichment of one of the alloying elements, or depletion of one of these elements in the grain-boundary areas. Small amounts of iron in aluminum, wherein the solubility of iron is low, have been shown to segregate in the grain boundaries and cause intergranular corrosion. It has been shown that based on surface tension considerations the zinc content of a brass is higher at the grain boundaries. Depletion of chromium in the grain-boundary regions results in intergranular corrosion of stainless steels.(back to top) Stress-corrosion cracking Stress-corrosion cracking refers to cracking caused by the simultaneous presence of tensile stress and a specific corrosive medium. Many investigators have classified all cracking failures occurring in corrosive mediums as stress-corrosion cracking, including failures due to hydrogen embrittlement. However, these two types of cracking failures respond differently to environmental variables. To illustrate, cathodic protection is

an effective method for preventing stress-corrosion cracking whereas it rapidly accelerates hydrogen-embrittlement effects. Hence, the importance of considering stress-corrosion cracking and hydrogen embrittlement as separate phenomena is obvious. For this reason, the two cracking phenomena are discussed separately in this chapter. During stress-corrosion cracking, the metal or alloy is virtually unattacked over most of its surface, while fine cracks progress through it. This cracking phenomenon has serious consequences since it can occur at stresses within the range of typical design stress. Exposure to boiling MgCl2 at 310F (154C) is shown to reduce the strength capability to approximately that available at 1200F. The two classic cases of stress-corrosion cracking are "season cracking" of brass, and the "caustic embrittlement" of steel. Both of these obsolete terms describe the environmental conditions present which led to stresscorrosion cracking. Season cracking refers to the stress-corrosion cracking failure of brass cartridge cases. During periods of heavy rainfall, especially in the tropics, cracks were observed in the brass cartridge cases at the point where the case was crimped to the bullet. It was later found that the important environmental component in season cracking was ammonia resulting from the decomposition of organic matter. Many explosions of riveted boilers occurred in early steam-driven locomotives. Examination of these failures showed cracks or brittle failures at the rivet holes. These areas were cold-worked during riveting operations, and analysis of the whitish deposits found in these areas showed caustic, or sodium hydroxide, to be the major component. Hence, brittle fracture in the presence of caustic resulted in the term caustic embrittlement. While stress alone will react in ways well known in mechanical metallurgy (i.e., creep, fatigue, tensile failure) and corrosion alone will react to produce characteristic dissolution reactions; the simultaneous action of both sometimes produces the disastrous results.

EFFECTS OF CORROSION Loss of economy and safety Reduced Strength Downtime of equipment Escape of fluids Lost surface properties Reduced value of goods

The consequences of corrosion are many and varied and the effects of these on the safe, reliable and efficient operation of equipment or structures are often more serious than the simple loss of a mass of metal. Failures of various kinds and the need for expensive replacements may occur even though the amount of metal destroyed is quite small. This calls on for the need to protect/control various metals from corrosion.

WAYS TO CONTROL CORROSION a) HUMIDITY Control the level of humidity around the metal. For example, Water reacts with iron to form carbonic acid, which breaks down the bonds of the iron. At the same time, at least some of the water is broken up into hydrogen and oxygen. When iron comes in contact with the oxygen from the water, the oxygen and iron bond to form iron oxide (rust). By keeping the humidity level low around an object containing iron, the amount of corrosion that will occur is minimized. Dehumidifiers are a simple, inexpensive way to control the humidity in a confined environment. b) PAINT Coat the surface of the metal with a corrosion-resistant paint. The paint will serve as a barrier between the metal and the moisture and other corrosive agents that can come in contact with it. With such a barrier in place, the chemical reactions that leads to the formation of oxides, sulphides,

carbonates etc:- on the surface of the metal are deterred. But since paint wears away over time, the surface must be repainted regularly. c) OIL / GREASE / TAR / PLASTIC Like paint, oil also acts as a protective barrier between the metal surface and corrosive agents. This method works best for small objects, such as iron tools, but it also can be used for small parts of larger structures, such as iron bolts. d) SACRIFICIAL PROTECTION This process involves the enclosement of a metal to be protected with a more reactive metal which will corrode first, thus protecting the lower layer. 'Rusting' can be prevented by connecting iron to a more reactive metal (e.g., zinc or magnesium). This is referred to as sacrificial protection or sacrificial corrosion, because the more reactive protecting metal is preferentially oxidized away, leaving the protected metal intact. e) ALLOYING Metals can also be protected by 'alloying' or mixing with other metals (e.g., chromium) to make non-rusting alloys. Stainless steel is an example of a nonrusting alloy of iron and carbon. Brass, an alloy containing copper is another metal alloy which is less expensive and non reactive. f) GALVANIZING Coating iron or steel with a thin zinc layer is called 'galvanizing'. This layer is produced by electrolytic deposition. Dipping the iron/steel object in molten zinc and using it as the negative cathode zinc is coated on it. Zinc preferentially corrodes or oxidizes to form a zinc oxide layer that does not flake off like iron oxide rust. Also, if the surface is scratched, the exposed zinc again corrodes before the iron and continues to protect it. g) ELECTROPLATING Coating the surface with metals like tin, chromium, nickel etc. by electroplating is also utilized to prevent corrosion. Steel cans are protected

by relatively un-reacted tin and works well as long as the thin tin layer is complete. p.s.

Uniform corrosion The reaction starts at the surface and proceeds uniformly.

Localized corrosion (pitting corrosion) The basis metal is eaten away and perforated in places in the manner of holes, the rest of the surface being affected only slightly or not at all.

Wide pitting corrosion The corrosion causes localized scarring.

Intergranular corrosion Imperceptible or barely perceptible from outside, since the corrosion proceeds at the grain boundaries.

Transgranular or intragranular corrosion The grain boundary material is retained, since the corrosion proceeds preferentially within the grain.

Galvanic corrosion Increased corrosion in crevices or cracks or at contact surfaces between two metal articles.

Selective corrosion

Exfoliation corrosion

Interfacial corrosion

Corrosive attack on structural constituents

Occurs in deformed articles. Corrosion follows "fiber orientation".

Frequently observed at water-air interfaces.

corrosion

Anodic coating

galvanising

electroplating

Sacrificial protection

TYPES OF CORROSION

Pitting corrosion is a form of extremely localized corrosion that leads to the creation of small holes in the metal. The driving power for pitting corrosion is the depassivation of a small area, which becomes anodic while an unknown but potentially vast area becomes cathodic, leading to very localized galvanic corrosion. The corrosion penetrates the mass of the metal, with limited diffusion of ions. The mechanism of pitting corrosion is probably the same as crevice corrosion. Pitting can be initiated by a small surface defect, being a scratch or a local change in composition, or a damage to protective coating. Polished surfaces display higher resistance to pitting.

For example, metals like stainless steel and aluminium which are normally protected by a thin oxide film, are subjected to pitting corrosion in a chloride environment, thus making its unsuitable for in use in a sea water system.

Classification of Corrosion

Based on the mechanism of corrosion, it is classified into two types 1. Chemical or dry corrosion 2. Electrochemical or wet corrosion Dry corrosion:

Corrosion takes place in dry state.

In occurs due to the direct chemical attack of the metal by the environment. Corrosion products accumulate on the same spot, where corrosion occurs. Dry corrosion is self controlled. It follows absorption mechanism. Homogenous metal surface undergoes corrosion observed.

Uniform corrosions are observed. Example: Formation of mild iron oxide on its surface. Dry corrosion is a form of corrosion, that occurs at elevated temperature without a liquid phase. Its a high temperature oxidation reaction. Wet corrosion:

Corrosion takes place in the presence of moisture. It occurs due to the setting up of large numbers of galvanic cells. Corrosion products accumulate on cathode.

Wet corrosion is continuous process.

It follows electrochemical mechanism. Heterogeneous metals bimetallic surface is the condition for corrosion.

Pitting corrosions are observed. Example: Formation of rust on iron under moist atmosphere. Wet corrosion means that there is a liquid phase, for example condensed humidity, in contact with metal. Its the most common form of corrosion.

Some Types of Corrosion

1. Galvanic or Bimetallic corrosion

Example: Zinc and copper, zinc forms the anode and is attacked and gets dissolved, whereas copper acts as cathode.

DRY CORROSION

WET CORROSION

RUSTING OF IRON

GALVANIC CORROSION When 2 different metals or alloys come in contact with each other, the less noble metal corrodes protecting the other cathodically. This phenomenon is called galvanic corrosion. Galvanic corrosion occurs when 2 different metals are electrically connected and are immersed in an electrolyte. In order for galvanic corrosion to occur, an electrically and ionically conductive path is necessary. This effects a galvanic couple where the more active metal corrodes at an accelerated rate and the more noble metal corrodes at a retarded rate. Galvanic corrosion is often utilized in sacrificial anodes. For example zinc is often used as a sacrificial anode for steel structure like pipelines. Factors such as relative size of anode (smaller is preferred), type of metal and operating conditions (temp, humidity), affect galvanic corrosion.

PITTING CORROSION

INTERGRANULAR CORROSION Intergranular corrosion is the phenomenon in which there is increased rate of corrosion along the grain boundaries rather than at the grain interior. Grains are crystals usually on a microscopic scale, that constitute the (micro)structure of metals and alloys. This selective dissolution may lead to the dislodgement of grains. Some significant examples include Intergranular corrosion in sensitized stainless steels and exfoliation in aluminium alloys etc:At the temperature range of 450-850 oC carbon diffuses to the grain boundary of stainless steel and reacts with chromium to precipitate chromium carbide. But for stainless steel, the corrosion resistance depends on the Cr content which due to depletion increases the susceptibility to corrosion.

WATER LINE CORROSION It is generally found that when water is stored in a steel tank, the maximum corrosion occurs along a line just beneath the water meniscus. This is because of the fact that the highly oxygenated area above the waterline acts as the cathodic part, while the portion just below the waterline act as the anodic part undergoing corrosion. This type of corrosion is commonly seen in water tanks, base of ships etc:STRESS CORROSION (figure 3.4 from page 3.6) Stress corrosion is the part of tensile stress (including residual stress remaining after fabrication) and localized corrosion which combine to produce a brittle cracking of metal under certain conditions. During stresscorrosion cracking, the metal or alloy is virtually unattacked over most of its surface, while fine cracks progress through it. It generally has serious consequences.

The stresses can be internal or applied. An example is that of brass condenser tubes. The reason for this is the moist atmosphere containing ammonia. The attack is along the grain boundaries which become more anodic with respect to grain interior.

CONCENTRATION CELL CORROSION This corrosion is also known as differential aeration corrosion. It occurs when a metal is partially immersed in a solution or when partially covered by water drops, dust, sand etc:- Its often combined with stagnant fluid or in areas with low fluid velocity. Here the more aerated area acts as the cathode, while the less aerated area acts as the anode undergoing corrosion. There are 3 general types of concentration cell corrosion: > Metal ion concentration cell > Oxygen concentration cell > Active- passive concentration cell The common examples in this type of corrosion include corrosion of heater handles, knives etc:-

MICROBIOLOGICAL CORROSION Microbiological corrosion is that caused / promoted by microorganisms. It can apply to both metals and non-metals, in both presence (aerobic) and in lack of oxygen (anaerobic). The bacterial activities can -> produce a corrosive environment, -> alter metal films resistance, -> create electrolytic concentration cells on the metal surface, -> affect rate of cathodic and anodic reaction. Sulphate reducing bacteria are common in lack of oxygen. They produce hydrogen sulphide, causing sulphide stress cracking. In presence of oxygen some bacteria directly oxidize iron to iron oxides and hydroxides, other bacteria oxidize sulphur and produce sulphuric acid causing biogenic sulphide corrosion. Microbes like fungi, algae etc:- develop a microbiological film on iron surfaces. Such films can contain dissolved salts, acids etc:- thereby creating local biological cells to accelerate corrosion.

WET CORROSION

RUSTING OF IRON

GALVANIC CORROSION

PITTING CORROSION

SHAPES OF PITTING CORROSION

OXYGEN CONCENTRATION CELL

INTERGRANULAR CORROSION

STRESS CORROSION

Concentration cell corrosion

OXYGEN CONCENTRATION CELL