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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 Faradays 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.
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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. Since transfer of electrons involves transfer of charge and is termed as current, the potential/driving force which makes the reaction happen is given an electrical term of Electrochemical Potential. 1.3 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 + O2 + 2e- 2 OH (3)

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Reaction 2 is most common in acids and in the pH range 6.5 8.5 the most important reaction is oxygen reduction 3. In this latter case corrosion is usually accompanied by the formation of solid corrosion debris from the reaction between the anodic and cathodic products. Fe
2+

+ 2 OH Fe(OH)2 , 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. 2 Fe(OH)2 + H2O + O2 2 Fe(OH)3 , 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. 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. 4 Fe(OH)2(s) + O2(g) 2 Fe2O3 H2O(s) + 2 H2O (Rust) 1.4 TYPES OF CORROSION Corrosion is classified under two categories. 1. Uniform Corrosion 2. Localized Corrosion 1.4.1 UNIFORM CORROSION Uniform or general corrosion, is a corrosion process without appreciable localized attack. 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. 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.

1.4.2 LOCALISED CORROSION The consequences of localized corrosion can be a great deal, more severe than uniform corrosion generally because the failure occurs without warning and after a surprisingly short period of use or exposure. Application of the five basic facts needs greater thought and insight. 1. Galvanic Corr osion Galvanic corrosion, bimetallic corrosion, occurs when two electrochemically dissimilar metals are metallically connected and exposed to a corrosive environment. 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. On the galvanic scale, aluminum and zinc are more active than steel and in the presence of a chloridecontaining electrolyte, will corrode preferentially when in contact with steel. Three special features of this mechanism need to operate for corrosion to occur: The metals need to be in contact electrically. One metal needs to be significantly better at giving up electrons than the other. An additional path for ion and electron movement is necessary.

The galvanic corrosion mechanism can be used beneficially. It is widely employed as the Primary protection system for steel. A thin coating of zinc on steel will corrode preferentially, and this sacrificial action provides long-term protection for the steel substrate.

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

INTERGRANULAR

TRANSGRANULAR

6. Dealloying Dealloying is a corrosion process in which one element is preferentially removed from an alloy. This occurs without appreciable change in the size or shape of the component; but the affected area becomes weak, brittle, and porous. The two most important examples of dealloying are the preferential removal of zinc from copper zinc alloys (dezincification), and the preferential removal of iron from gray-cast iron (graphitic corrosion). Graphitic corrosion sometimes occurs on underground cast iron water mains and leads to splitting of the pipe when the water pressure is suddenly increased. 7. Erosion corr osion. Erosion corrosion refers to the repetitive formation (a corrosion process) and destruction (a mechanical process) of the metal's protective surface film. This typically occurs in a
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moving liquid. Erosion may be impinging (in the case of a pipe ell) or sliding (pipe wall) when it occurs. An example is the erosion corrosion of copper water tubes in a hot, high velocity, soft water environment. Cavitation is a special form of erosion corrosion. 1.5 CORROSING PREVENTION In practical terms it is not usually possible to eliminate completely all corrosion damage to metals used for the construction. By retarding either the anodic or cathodic reactions the rate of corrosion can be reduced. This can be achieved in several ways: 1.5.1 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. The coating may consist of: Another metal, e.g. zinc or tin coatings on steel, A protective coating derived from the metal itself, e.g. aluminum oxide on anodised aluminum, Organic coatings, such as resins, plastics, paints, enamel, oils and greases. The action of protective coatings is often more complex than simply providing a barrier between metal and environment. Paints may contain a corrosion inhibitor or zinc coating on iron or steel confers cathodic protection. (b) Alloying the metal To produce a more corrosion resistant alloy, e.g. stainless steel, in which ordinary steel is alloyed with chromium and nickel. Stainless steel is protected by an invisibly thin, naturally formed film of chromium sesquioxide Cr2O3. 1.5.2 Conditioning the Corr osive Environment (a) Removal of Oxygen By the removal of oxygen from water systems in the pH range 6.5-8.5 one of the components required for corrosion would be absent. The

removal of oxygen could be achieved by the use of strong reducing agents e.g. sulphite. (b) Corr osion Inhibitors A corrosion inhibitor is a chemical additive, which, when added to a corrosive aqueous environment, reduces the rate of metal wastage. It can function in one of the following ways: 1. Anodic inhibitors as the name implies an anodic inhibitor interferes with the inhibitors. Examples of anodic inhibitors include orthophosphate, nitrite, ferricyanide and silicates. 2. Cathodic inhibitors Additives that suppress cathodic reactions called cathodic inhibitors. They function by reducing the available area for the cathodic reaction. This is often achieved by precipitating an insoluble species onto the cathodic sites. 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. Cathodic inhibitors are classed as safe because they do not cause localized corrosion. 3. Adsorption type corrosion inhibitors Many organic inhibitors work by an adsorption mechanism. 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. The main functional groups capable of forming chemisorbed bonds with metal surfaces are amino (-NH2), carboxyl (-COOH), and phosphonate (-PO3H2) although other functional groups or atoms can form co-ordinate bonds with metal surfaces. 4. Mixed inhibi tors Because of the danger of pitting when using anodic inhibitors alone, 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. This observation is generally referred to a synergism and demonstrates the synergistic action which exists between zinc and chromate ions. (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.
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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. The external anode may be a galvanic anode, where the current is a result of the potential difference between the two metals, or it may be an impressed current anode, where the current is impressed from an external dc power source. In electro-chemical terms, the electrical potential between the metal and the electrolyte solution with which it is in contact is made more negative, by the supply of negative charged electrons, to a value at which the corroding (anodic) reactions are stifled and only cathodic reactions can take place. In the discussion that follows it is assumed that the metal to be protected is carbon steel, which is the most common material used in construction. The cathodic protection of reinforcing carbon steel in reinforced concrete structures can be applied in a similar manner. Cathodic protection can be achieved in two ways: Use of galvanic (sacrificial) anodes Use of impressed current. 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, as indicated by their relative positions in the galvanic series, causes a positive current to flow in the electrolyte, from the anode to the steel. 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. The Galvanic Series should not be confused with the Electrochemical Series, which lists the potentials only of pure metals in equilibrium with standard solutions of their ions. Thus, the whole surface of the steel becomes more negatively charged and becomes the cathode. The metals commonly used, as sacrificial anodes are aluminum, zinc and magnesium. These metals are alloyed to improve the long-term performance and dissolution characteristics. Similar protection is obtained when steel is coated with a layer of zinc. 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.

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. The connections are similar for the application of cathodic protection to metallic storage tanks, jetties, offshore structures and reinforced concrete structures.

Impressed Current System