1 INTRODUCTION Steel is a suitable construction material for a wide range of structures because of its favorable mechanical properties and high speed fabrication. Corrosion may lead to damage of unprotected steel exposed in different environmental conditions. Corrosion is an electrochemical reaction process which leads to continuous loss of metal or metal alloys. Energy is needed to extract metals from their mineral state to the pure state. The same amount of energy is emitted during the formation of its chemical compounds or in other words during the process of corrosion. Corrosion returns the metal to its combined state in chemical compounds that are similar or even identical to the minerals from which the metals were extracted .Thus corrosion has been called extractive metallurgy in reverse. 1.2 MECHANISM OF CORROSION Corrosion reactions are electrochemical in nature. Surface of iron goes into solution as ferrous ions at anodic sites. Iron atoms undergoes oxidation to ions they release electron whose negative charge will quickly buildup in the metal and prevent anodic reaction, or corrosion Corrosion returns the metal to its combined state in chemical compounds that are similar or even identical to the minerals from which the metals were extracted. Thus corrosion has been called extractive metallurgy in reverse. The dissolution will only continue if the electrons released can pass to a site on the metal surface where a cathodic reaction is possible. At a cathodic site the electrons react with some reducible component of the electrolyte and are themselves removed from the metal. The rates of the anodic and cathodic reactions must be equivalent according to Faraday’s Laws, being determined by the total flow of electrons from anodes to cathodes which is called the “corrosion current”, ICorr. Since the corrosion current must also flow through the electrolyte by ionic conduction the conductivity of the electrolyte will influence the way in which corrosion cells operate.


3 CORROSION CHEMISTRY The most common and important electrochemical reactions in the corrosion of iron are Thus Fe → Fe + 2+ + 2e- Anodic reaction (corrosion) (1) Cathodic reactions (simplified) (2) 2 H → H2 + 2e- H2O + ½ O2 + 2e. the potential/driving force which makes the reaction happen is given an electrical term of Electrochemical Potential.Corrosion Mechanism The corroding part of metal is described as a “mixed electrode” since simultaneous anodic and cathodic reactions are proceeding on its surface. The mixed electrode is a complete electrochemical cell on metal surface. 1.→ 2 OH‾ (3) 2 . Since transfer of electrons involves transfer of charge and is termed as current.

5 the most important reaction is oxygen reduction 3. It the most common form of corrosion and may appear initially as a single penetration but with thorough examination of the cross section it becomes apparent that the base metal has uniformly thinned. Because the rust is precipitated as a result of secondary reactions it is porous and absorbent and tends to act as a sort of harmful poultice which encourages further corrosion. In this latter case corrosion is usually accompanied by the formation of solid corrosion debris from the reaction between the anodic and cathodic products.1 UNIFORM CORROSION Uniform or general corrosion. Uniform Corrosion 2.4 TYPES OF CORROSION Corrosion is classified under two categories. iron (II) hydroxide Pure iron (II) hydroxide is white but the material initially produced by corrosion is normally a greenish color due to partial oxidation in air.4. 3 .Reaction 2 is most common in acids and in the pH range 6. 4 Fe(OH)2(s) + O2(g) → 2 Fe2O3 •H2O(s) + 2 H2O (Rust) 1. Fe 2+ + 2 OH‾ → Fe(OH)2 . Hydrated iron (III) oxide Further hydration and oxidation reactions can occur and the reddish rust that eventually forms is a complex mixture whose exact constitution will depend on other trace elements which are present. Corrosion is uniform if the time average of the corrosion current through a unit area of any macroscopic dimension is independent of the position on the surface. 2 Fe(OH)2 + H2O + ½ O2 → 2 Fe(OH)3 . Localized Corrosion 1. 1. is a corrosion process without appreciable localized attack.5 – 8.

The less noble metal(anode) suffers accelerated attack and the less noble metal (cathode) is cathodically protected by the galvanic current. The tendency of a metal to corrode in a galvanic cell is determined by its position in the galvanic series. A thin coating of zinc on steel will corrode preferentially. occurs when two electrochemically dissimilar metals are metallically connected and exposed to a corrosive environment. One metal needs to be significantly better at giving up electrons than the other. 1.4. On the galvanic scale. An additional path for ion and electron movement is necessary. 4 . Three special features of this mechanism need to operate for corrosion to occur: • • • The metals need to be in contact electrically. Galvanic Corr osion Galvanic corrosion. will corrode preferentially when in contact with steel. Application of the five basic facts needs greater thought and insight. and this sacrificial action provides long-term protection for the steel substrate. aluminum and zinc are more active than steel and in the presence of a chloridecontaining electrolyte.2 LOCALISED CORROSION The consequences of localized corrosion can be a great deal. The galvanic corrosion mechanism can be used beneficially. bimetallic corrosion.1. more severe than uniform corrosion generally because the failure occurs without warning and after a surprisingly short period of use or exposure. It is widely employed as the Primary protection system for steel.

threaded joints. This form of corrosion is sometimes referred to as “crevice corrosion. or overheating 10 5 . the grain boundaries of an alloy. lap joints. Normal mechanical construction can create crevices at sharp corners. most problems encountered in service involve austenitic stainless steels (such as 304 and 316) and the 2000 and 7000 series aluminum alloys. fasteners. Pitting corrosion is a randomly occurring. yet its mechanism is not completely understood. Pitting is one of the most destructive forms of corrosion. spot welds. At least five types of concentration cells exist. Concentration-cell corrosion occurs because of differences in the environment surrounding the metal. Pitting corr osion. Various grades of stainless steel are susceptible to pitting corrosion when exposed to saline environments. Intergranul ar corrosion Intergranular corrosion isa localized condition that occurs at. Welding. Although a number of alloy systems are susceptible to intergranular corrosion. Concentration-cell corrosion. flanged fittings. improper heat treating. Areas on a surface in contact with an electrolyte having a high oxygen concentration generally will be cathodic relative to those areas where less oxygen is present (oxygen cell). couplings. 4. or in narrow zones immediately adjacent to.” “gasket corrosion. highly localized form of attack on a metal surface.2. Steel and galvanized steel pipes and storage tanks are susceptible to pitting corrosion and tuberculation by many potable waters. Areas on a surface where the electrolyte contains an appreciable quantity of the metal’s ions will be cathodic compared to locations where the metal ion concentration is lower (metal ion cell). 3. characterized by the fact that the depth of penetration is much greater than the diameter of the area affected . and tube sheet supports. stress relief annealing.” and “deposit corrosion” because it commonly occurs in localized areas where small volumes of stagnant solution exist. the most common are the “oxygen” and “metal ion” cells.

brittle.in service generally establish the microscopic. compositional in homogeneities that make a material susceptible to intergranular corrosion. Erosion corr osion. 7. it can happen ‘unexpectedly’ and rapidly after a period of satisfactory service leading to catastrophic failure of structures or leaks in pipe work. The two most important examples of dealloying are the preferential removal of zinc from copper zinc alloys (dezincification). Erosion corrosion refers to the repetitive formation (a corrosion process) and destruction (a mechanical process) of the metal's protective surface film. Dealloying Dealloying is a corrosion process in which one element is preferentially removed from an alloy. and porous. This typically occurs in a 6 . Stress corrosion cracking SCC (environmentally induced delayed failure) describes the phenomenon that can occur when many alloys are subjected to static. surface tensile stresses and are exposed to certain corrosive environments. 5. and the preferential removal of iron from gray-cast iron (graphitic corrosion). This is specific to a metal material paired with a specific environment. Examples of well-known material/environment pairs are: INTERGRANULAR TRANSGRANULAR 6. Because. but the affected area becomes weak. Graphitic corrosion sometimes occurs on underground cast iron water mains and leads to splitting of the pipe when the water pressure is suddenly increased. This occurs without appreciable change in the size or shape of the component.

moving liquid. Paints may contain a corrosion inhibitor or zinc coating on iron or steel confers cathodic protection. Stainless steel is protected by an invisibly thin. e. • A protective coating derived from the metal itself. (b) Alloying the metal To produce a more corrosion resistant alloy. aluminum oxide on “anodised” aluminum.5.5.g. oils and greases. The 7 . • Organic coatings. enamel. naturally formed film of chromium sesquioxide Cr2O3.5-8.2 Conditioning the Corr osive Environment (a) Removal of Oxygen By the removal of oxygen from water systems in the pH range 6. This can be achieved in several ways: 1. e. zinc or tin coatings on steel. By retarding either the anodic or cathodic reactions the rate of corrosion can be reduced. such as resins. Cavitation is a special form of erosion corrosion.g. 1.5 CORROSING PREVENTION In practical terms it is not usually possible to eliminate completely all corrosion damage to metals used for the construction.5 one of the components required for corrosion would be absent. in which ordinary steel is alloyed with chromium and nickel.1 Conditioning the Metal This can be sub-divided into two main groups: (a) Coating the metal In order to interpose a corrosion resistant coating between metal and environment. 1. Erosion may be impinging (in the case of a pipe ell) or sliding (pipe wall) when it occurs. The action of protective coatings is often more complex than simply providing a barrier between metal and environment. The coating may consist of: • Another metal. An example is the erosion corrosion of copper water tubes in a hot.g. high velocity. plastics. paints. soft water environment. e. stainless steel.

The resultant film of chemisorbed inhibitor is then responsible for protection either by physically blocking the surface from the corrosion environment or by retarding the electrochemical processes. Cathodic inhibitors are classed as safe because they do not cause localized corrosion. 2. This is often achieved by precipitating an insoluble species onto the cathodic sites. Cathodic inhibitors– Additives that suppress cathodic reactions called cathodic inhibitors. Examples of anodic inhibitors include orthophosphate. (c) Electrochemical Control/Cathodic Protection Since corrosion is an electrochemical process its progress may be studied by measuring the changes which occur in metal potential with time or with applied electrical currents.removal of oxygen could be achieved by the use of strong reducing agents e. when added to a corrosive aqueous environment. it became common practice to incorporate a cathodic inhibitor into formulated performance was obtained by a combination of inhibitors than from the sum of the individual performances. reduces the rate of metal wastage. They function by reducing the available area for the cathodic reaction. Anodic inhibitors – as the name implies an anodic inhibitor interferes with the inhibitors. and phosphonate (-PO3H2) although other functional groups or atoms can form co-ordinate bonds with metal surfaces. 4.g. 3. This observation is generally referred to a ‘synergism’ and demonstrates the synergistic action which exists between zinc and chromate ions. Adsorption type corrosion inhibitors – Many organic inhibitors work by an adsorption mechanism. carboxyl (-COOH). 8 . (b) Corr osion Inhibitors A corrosion inhibitor is a chemical additive. Mixed inhibi tors – Because of the danger of pitting when using anodic inhibitors alone. Zinc ions are used as cathodic inhibitors because of the precipitation of Zn(OH)2 at cathodic sites as a consequence of the localized high pH. nitrite. It can function in one of the following ways: 1. The main functional groups capable of forming chemisorbed bonds with metal surfaces are amino (-NH2). ferricyanide and silicates. sulphite. which.

which lists the potentials only of pure metals in equilibrium with standard solutions of their ions. Cathodic protection can be achieved in two ways: • Use of galvanic (sacrificial) anodes • Use of “impressed” current. The Galvanic Series should not be confused with the Electrochemical Series. causes a positive current to flow in the electrolyte. the electrical potential between the metal and the electrolyte solution with which it is in contact is made more negative. which is the most common material used in construction. Similar protection is obtained when steel is coated with a layer of zinc. zinc and magnesium. by the supply of negative charged electrons. The metals commonly used. These metals are alloyed to improve the long-term performance and dissolution characteristics. Galvanic effects may be predicted by means of a study of the Galvanic Series which is a list of metals and alloys placed in order of their potentials in the corrosive environment. such as sea water. where the current is impressed from an external dc power source.The principle of cathodic protection is in connecting an external anode to the metal to be protected and the passing of an electrical dc current so that all areas of the metal surface become cathodic and therefore do not corrode. Even at scratches or cut edges where some bare metal is exposed the zinc is able to pass protective current through the thin layer of surface moisture. as sacrificial anodes are aluminum. where the current is a result of the potential difference between the two metals. or it may be an impressed current anode. In electro-chemical terms. The external anode may be a galvanic anode. In the discussion that follows it is assumed that the metal to be protected is carbon steel. the whole surface of the steel becomes more negatively charged and becomes the cathode. as indicated by their relative positions in the galvanic series. The cathodic protection of reinforcing carbon steel in reinforced concrete structures can be applied in a similar manner. Thus. Galvanic anode systems employ reactive metals as auxiliary anodes that are directly electrically connected to the steel to be protected. The difference in natural potentials between the anode and the steel. to a value at which the corroding (anodic) reactions are stifled and only cathodic reactions can take place. from the anode to the steel. 9 .

offshore structures and reinforced concrete structures.Impressed-current systems employ inert (zero or low dissolution) anodes and use an external source of dc power (rectified ac) to impress a current from an external anode onto the cathode surface. jetties. Impressed –Current System . The connections are similar for the application of cathodic protection to metallic storage tanks.

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