WHAT IS CORROSION? Corrosion is the chemical or electrochemical reaction between a metal and its environment.

It can also be regarded as the degradation of a material due to a reaction with its environment. Degradation implies deterioration of the physical properties of the material. The material can be metals, polymers (plastics, rubbers etc), ceramics (concrete, bricks etc) or composites-mechanical mixtures of two or more materials with different properties. Because metals are the most used type of structural materials this lecture will be devoted to the corrosion of metals. CONSEQUENCES OF CORROSION The consequences of corrosion are varied and the effects of these on the safe, reliable and efficient operation of the 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. Some of the major harmful effects of corrosion can be summarized as follows: Hazards or injuries to people arising from structural failure or breakdown (e.g. bridges,cars,aircraft) Reduced value of goods due to deterioration of appearance Reduction of metal thickness leading to loss of mechanical strength and structural failure or breakdown. Mechanical damage to valves, pumps etc or blockage of pipes by solid corrosion products. Loss of technically important surface properties of a metallic component. These could include frictional and bearing properties, ease of flow over a pipe surface, electrical conductivity of contacts, surface reflectivity or heat transfer across a surface. Contamination of fluids in vessels and pipes (e.g. beer goes cloudy when small quantities of heavy metals are released by corrosion)

CHEMISTRY OF CORROSION Firstly, we shall review our understanding of the nature of Matter (i.e. Atoms, Ions, molecules) Atoms: All matter is made up of atoms composed of protons, neutrons and electrons. The center or nucleus of the atom is composed of positively charged protons and neutrons. The outside of the atom has negatively charged electrons in various orbits. This is shown schematically in the figure below

All the atoms of an element have the same number of protons and electrons; hence the atom is electrically stable. The number of protons in the atom is called the atomic number ( Np)while the sum of the protons and neutrons in the atom gives the atomic mass (A) of the element. Every element is represented by a chemical symbol. For example, H stands for Hydrogen, C for carbon Na for Sodium, Fe for Iron A typical atom is represented chemically in this form:

Where the subscript is the atomic number and superscript the atomic mass. Ions: Ions are formed when atoms or group of atoms lose or gain electrons. Metals lose some of their electrons to form positively charged ions, e.g. Fe+2, Al+3, Cu+2, etc Non metals gain electrons and form negatively charged ions e.g. Cl-, O-2, OH-, etc Molecules: Compounds are groups of metal s and nonmetals that form distinct chemicals. Most of us are familiar with the formula H2O, which indicates that each water molecule is made up two hydrogen atoms and one oxygen atom. Many molecules are formed by sharing electrons between adjacent atoms. A water molecule has adjacent hydrogen and oxygen atoms sharing some of their electrons.

ELECTROCHEMICAL CELLS Oxidation and Reduction: Metals are elements that tend to lose electrons when they are involved in chemical reactions, and nonmetals are those element s that tend to gain electrons. Sometimes these elements form ions, charged elements or groups of elements. Metallic ions, because they are formed from atoms that have lost electrons, are positively charged (the nucleus is unchanged). When an atom or ions loses electrons it is said to have been oxidized. So

oxidation could be define as the loss of electron(s)

A common oxidation reaction in corrosion is the oxidation of neutral sodium atoms to positively charged iron ions: Na (1) The electrons lost from a metal must go somewhere, and they usually end up on a nonmetallic atom forming a negatively charged nonmetallic ion. The atom that gained the electron(s) is said to have been reduced. Hence, reduction is the gain of electron(s) Cl + e(2) CAUSES OF CORROSION Corrosion occurs by an electrochemical process. The Phenomenon is similar to that which takes place when a carbon- zinc dry cell generates a direct current. Basically, an anode (negative electrode).a cathode (positive electrode) an electrolyte (environment) and a circuit connecting the anode and the cathode are required for corrosion to occur .Dissolution of metal occurs at the anode where the corrosion current enters the electrolyte and flows to the cathode. Equation (1) shows what happens at the anode. Examination of that reaction reveals that oxidation occurs at the anode. Electrons lost at the anode flow through the metallic circuit to the cathode and permit a cathodic reaction to occur. The most common and important electrochemical reactions in the corrosion of iron are thus Anodic reaction (corrosion) Fe Fe2+ + 2eClNa+ + eor Na - eNa+

The cathodic reaction that usually occurs in deaerated acids is 2H+ + 2eH2

In alkaline (basic) and neutral aerated solutions, the predominant cathodic reaction is O2 + 2H2O + 4e4(OH)

In this latter case corrosion is usually accompanied by the formation of solid corrosion debris from the reaction between the anodic and cathodic products Fe2+ + 2OHFe(OH)2 , iron (II) hydroxide

Pure iron (II) hydroxide is white but the material initially produced by corrosion is normally a greenish colour due to partial oxidation in air. 4Fe (OH)2 + 2 H2O + O2 4Fe (OH)3 , hydrated iron (III) oxide

Further hydration and oxidation reactions can occur and the reddish rust that eventually forms is a complex mixture. The insoluble corrosion product is formed by a secondary chemical reaction. ELECTRODE POTENTIALS When a metal is immersed in an aqueous solution containing a definite concentration of ions, C, there is one electric potential(voltage) at which equilibrium can exist between the metal and the solution. The greater the negative potential, the greater is the tendency of a metal to dissolve. The electrode potential is given by the Nernst Equation: E = E0 + 0.0592/n Log C Where E0 =Standard Electrode Potential of the metal C = Concentration in kmol of ions N = valency of the ion in the equation Now for a solution containing 10-3 mol of Fe+2 per liter; E = -0.44 +(0.0592 /2) Log 10-3 E = -0.44 + (0.0296) (-3) E = -0.529V Nernst Equation is also given in natural logarithm thus E = E0 RT/nF Loge C

Where R =Universal gas constant (8.314KJ/Kg mol.K) T = Absolute temperature in K F = Faraday, which is the quantity of electricity that will liberate or deposit one mole of a substance during electrolysis. The standard electrode potential,E0 of metals are arrange in their order of increasing potential to form Galvanic, electrochemical or electromotive series. The ability of metals to resist corrosion is to some extent dependent upon their position in the electrochemical series. The farther two metals are separated from one another in the series, the more powerful is the electric current produced by their contact in the presence of an electrolyte. Also the more rapidly the lower metal is attacked, the more will the higher metal be protected.

FORMS OF CORROSION 1. General Corrosion This is also called general corrosion. The surface effect produced by most direct chemical attacks (e.g., as by an acid) is a uniform etching of the metal. On a polished surface, this type of corrosion is first seen as a general dulling of the surface and, if allowed to continue, the surface becomes rough and possibly frosted in appearance. The discoloration or general dulling of metal created by its exposure to elevated temperatures is not to be considered as uniform etch corrosion. The use of chemical-resistant protective coatings or more resistant materials will control these problems. While this is the most common form of corrosion, it is generally of little engineering significance, because structures will normally become unsightly and attract maintenance long before they become structurally affected. The facilities shown in the picture below show how this corrosion can progress if control measures are not taken.

2. Galvanic Corrosion Galvanic corrosion is an electrochemical action of two dissimilar metals in the presence of an electrolyte and an electron conductive path. It occurs when dissimilar metals are in contact. It is recognizable by the presence of a buildup of corrosion at the joint between the dissimilar metals. For example, when aluminum alloys or magnesium alloys are in contact with steel (carbon steel or stainless steel), galvanic corrosion can occur and accelerate the corrosion of the aluminum or magnesium.

This can be seen on the photo above where the aluminum helicopter blade has corroded near where it was in contact with a steel counterbalance. Galvanic Series In Sea Water Noble (least active) Platinum Gold Graphite Silver 18-8-3 Stainless steel, type 316 (passive) 18-8 Stainless steel, type 304 (passive) Titanium 13 percent chromium stainless steel, type 410 (passive) 7NI-33Cu alloy 75NI-16Cr-7Fe alloy (passive) Nickel (passive) Silver solder M-Bronze G-Bronze 70-30 cupro-nickel Silicon bronze

Copper Red brass Aluminum bronze Admiralty brass Yellow brass 76NI-16Cr-7Fe alloy (active) Nickel (active) Naval brass Manganese bronze Muntz metal Tin Lead 18-8-3 Stainless steel, type 316 (active) 18-8 Stainless steel, type 304 (active) 13 percent chromium stainless steel, type 410 (active) Cast iron Mild steel Aluminum 2024 Cadmium Alclad Aluminum 6053 Galvanized steel Zinc Magnesium alloys Magnesium Anodic (most active) The natural differences in metal potentials produce galvanic differences, such as the galvanic series in sea water. If electrical contact is made between any two of these materials in the presence of an electrolyte, current must flow between them. The farther apart the metals are in the galvanic series, the greater the galvanic corrosion effect or rate will be. Metals or alloys at the upper end are noble while those at the lower end are active. The more active metal is the anode or the one that will corrode. Control of galvanic corrosion is achieved by using metals closer to each other in the galvanic series or by electrically isolating metals from each other. Cathodic protection can also be used to control galvanic corrosion effects.

Electrical isolation flanges like those shown above are used to prevent galvanic corrosion. Insulating gaskets, usually polymers, are inserted between the flanges, and insulating sleeves and washers isolate the bolted connections. 3. Concentration Cell Corrosion Concentration cell corrosion occurs when two or more areas of a metal surface are in contact with different concentrations of the same solution. There are three general types of concentration cell corrosion:

1. metal ion concentration cells 2. oxygen concentration cells, and 3. active-passive cells. Metal Ion Concentration Cells

In the presence of water, a high concentration of metal ions will exist under faying surfaces and a low concentration of metal ions will exist adjacent to the crevice created by the faying surfaces. An electrical potential will exist between the two points. The area of the metal in contact with the low concentration of metal ions will be cathodic and will be protected, and the area of metal in contact with the high metal ion concentration will be anodic and corroded. This condition can be eliminated by sealing the faying surfaces in a manner to exclude moisture. Proper protective coating application with inorganic zinc primers is also effective in reducing faying surface corrosion. Oxygen Concentration Cells A water solution in contact with the metal surface will normally contain dissolved oxygen. An oxygen cell can develop at any point where the oxygen in the air is not allowed to diffuse uniformly into the solution, thereby creating a difference in oxygen concentration between two points. Typical locations of oxygen concentration cells are under either metallic or nonmetallic deposits (dirt) on the metal surface and under faying surfaces such as riveted lap joints. Oxygen cells can also develop under gaskets, wood, rubber, plastic tape, and other materials in contact with the metal surface. Corrosion will occur at the area of low-oxygen concentration (anode). The severity of corrosion due to these conditions can be minimized by sealing, maintaining surfaces clean, and avoiding the use of material that permits wicking of moisture between faying surfaces. Active-Passive Cells Metals that depend on a tightly adhering passive film (usually an oxide) for corrosion protection; e.g., austenitic corrosion-resistant steel, can be corroded by active-passive cells. The corrosive action usually starts as an oxygen concentration cell; e.g., salt deposits on the metal surface in the presence of water containing oxygen can create the oxygen cell. If the passive film is broken beneath the salt deposit, the active metal beneath the film will be exposed to corrosive attack. An electrical potential will develop between the large area of the cathode (passive film) and the small area of the anode (active metal). Rapid pitting of the active metal will result. This type of corrosion can be avoided by frequent cleaning and by application of protective coatings

4. Pitting Corrosion 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 d 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. Methods that can be used to control pitting include maintaining clean surfaces, application of a protective coating, and use of inhibitors or cathodic protection for immersion service. Molybdenum additions to stainless steel (e.g. in 316 stainless) are intended to reduce pitting corrosion.

The rust bubbles or tubercules on the cast iron above indicate that pitting is occurring. Researchers have found that the environment inside the rust bubbles is almost always

higher in chlorides and lower in pH (more acidic) than the overall external environment. This leads to concentrated attack inside the pits.

Similar changes in environment occur inside crevices, stress corrosion cracks, and corrosion fatigue cracks. All of these forms of corrosion are sometimes included in the term "occluded cell corrosion."

Pitting corrosion can lead to unexpected catastrophic system failure. The split tubing above left was caused by pitting corrosion of stainless steel. A typical pit on this tubing is shown above right. Sometimes pitting corrosion can be quite small on the surface and very large below the surface. The figure below left shows this effect, which is common on stainless steels and other film-protected metals. The pitting shown below right (white arrow) led to the stress corrosion fracture shown by the black arrows.

5. Crevice Corrosion Crevice corrosion refers to the localized attack on a metal surface at, or immediately adjacent to the gap or crevice between two joining surfaces. The gap or crevice can be formed between two metals or a non metallic material. Outside the gap or without the gap, both metals are resistant to corrosion. The damage is normally confined to one metal at localized area within or close to the joining surfaces The photo at the right is a stainless steel tube and tube sheet from a heat exchanger in a desalination plant that has suffered crevice corrosion due to the presence of crevice(gap) between the tube and tube sheet. Crevice is initiated by a difference in concentration of some chemical constituents, usually oxygen, which sets up an electrochemical concentration. Outside of the crevice(cathode),the oxygen content and pH are higher- but chlorides are lower. The chlorides concentrate inside the crevice (anode), worsening the situation. Crevices can be designed out of the system by welding continuously around a lap joint, the use of solid, non absorbent gasket such as Teflon etc. 6. Stress Corrosion Cracking Stress corrosion cracking (SCC) is caused by the simultaneous effects of tensile stress and a specific corrosive environment. Stresses may be due to applied loads, residual stresses from the manufacturing process, or a combination of both.

Cross sections of SCC frequently show branched cracks. This river branching pattern is unique to SCC and is used in failure analysis to identify when this form of corrosion has occurred. The photo below shows SCC of an insulated stainless-steel condensate line. Water wetted the insulation and caused chlorides to leach from the insulation onto the hot metal surface. This is a common problem on steam and condensate lines. Control is by maintaining the jackets around the lines so that moisture doesn't enter the insulation or is quickly drained off.

7. Erosion Corrosion corrosion is the result of a combination of an aggressive chemical environment and high fluid-surface velocities. This can be the result of fast fluid flow past a stationary object, such as the case with the oil-field check valve shown on the left below, or it can result from the quick motion of an object in a stationary fluid, such as happens when a ship's propeller churns the ocean.

Surfaces which have undergone erosion corrosion are generally fairly clean, unlike the surfaces from many other forms of corrosion. Erosion corrosion can be controlled by the use of harder alloys (including flame-sprayed or welded hard facings) or by using a more corrosion resistant alloy. Alterations in fluid velocity and changes in flow patterns can also reduce the effects of erosion corrosion. Erosion corrosion is often the result of the wearing away of a protective scale or coating on the metal surface. The oil field production tubing shown above on the right corroded when the pressure on the well became low enough to cause multiphase fluid flow. The impact of collapsing gas bubbles caused the damage at joints where the tubing was connected and turbulence was greater. Many people assume that erosion corrosion is associated with turbulent flow. This is true, because all practical piping systems require turbulent flow-the fluid would not flow fast enough if lamellar (non turbulent) flow were maintained. Most, if not all, erosion corrosion

can be attributed to multiphase fluid flow. The check valve on the left above failed due to sand and other particles in an otherwise noncorrosive fluid. The tubing on the right failed due to the pressure differences caused when gas bubbles collapsed against the pipe wall and destroyed the protective mineral scale that was limiting corrosion. 8. Intergranular Corrosion Intergranular corrosion is an attack on or adjacent to the grain boundaries of a metal or alloy. A highly magnified cross section of most commercial alloys will show its granular structure. This structure consists of quantities of individual grains, and each of these tiny grains has a clearly defined boundary that chemically differs from the metal within the grain center. Heat treatment of stainless steels and aluminum alloys accentuates this problem.

The picture above shows a stainless steel which corroded in the heat affected zone a short distance from the weld. This is typical of Intergranular corrosion in austenitic stainless steels. This corrosion can be eliminated by using stabilized stainless steels (321 or 347) or by using low-carbon stainless grades (304L or 3I6L). 9. Dealloying Dealloying is a process in which one element is preferentially removed from an alloy. This occurs without appreciable change in 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 (graphite corrosion).Graphite corrosion sometimes occurs on underground cast iron water mains and leads to splitting of the pipe when the water pressure is suddenly increased.

10. Microbial Corrosion This is a bio-corrosion arising from activities of sulphate reducing bacteria (SRB) in line pipe steels. SRB aided corrosion affects the internal surface of line pipe steels (Note O2 is absent).There are two ways in which micro-organisms are involved in corrosion processes. Firstly, by virtue of their growth and metabolism, they can introduce into an otherwise innocuous system, chemical entities such as acids,alkaline,sulphides and other aggressive ions which will render the environment corrosive .Secondly, their presence could provide the structure with a concentration cell with areas being anodic compound to the rest. Most instances of corrosion in the absence of oxygen have been attributed to SRB,namely desulfovibrio and desulfotomaculum.Typical examples of such environment are water heavily polluted with organic matter. These microbes are obligated anaerobes, that is they do not grow in the presence of even traces of oxygen but usually grow well at pH 5 and 9 and temperatures between 25oC and 44 oC. They utilize hydrogen or some reducing substance for their life process. The corrosion is often localized and is generally characterized by a black corrosion product with a strong smell of hydrogen sulphide (H2S).

CORROSION CONTROL MEASURES Corrosion mitigation can be accomplished by design considerations, by employing corrosion-resistant materials of construction, by employing cathodic protection, by using protective coatings and corrosion inhibitors Design considerations

The use of acceptable engineering practices to minimize corrosion is fundamental to corrosion control. This is accomplished by engineering design. One of the most important factors in designing for corrosion control is to avoid crevices where deposits of watersoluble compounds and moisture can accumulate and are not accessible for maintenance. Any region where two surfaces are loosely joined or come into proximity also qualifies as a crevice site. Joining geometries also present various crevice corrosion problems. Cathodic Protection

Cathodic protection is an electrical method of fighting against corrosion on metallic structures that are exposed to electrolyte such as soils and waters. Corrosion control is achieved by forcing a defined quantity of direct current to flow from auxiliary anodes, through the electrolyte, and onto the metal structure to be protected.Theoretically,corrosion of the structure is completely eliminated when the opencircuit potentials of the cathodic sites are polarized to the open circuit potentials of the anodic sites. The entire protected structure becomes cathodic relative to the auxiliary anodes. Therefore, corrosion of the metal structure will cease when the applied cathodic current equals the corrosion current. There are two basic methods of corrosion control by

cathodic protection. One involves the use of current that is produced when two electrochemically dissimilar metals or alloy are metallically connected and exposed to the electrolyte. This is commonly referred to as a sacrificial or galvanic cathodic protection system. The other method of cathodic protection involves the use of a direct current power source and auxiliary anodes, which is commonly referred to as an impressed current cathodic protection system. 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 electrochemical series, causes a positive current to flow in the electrolyte from the anode to the steel.Thus,the whole surface of the steel becomes more negatively charged and becomes the cathode. The metals commonly used, as sacrificial anodes are aluminuim,zinc and magnesium. These metals are alloyed to improve the long-term performance and dissolution characteristics. Advantages of Galvanic system Simple to install Independent of a source of external electric power Suitable for localised protection Less liable to cause interaction on neighbouring structures i.e. interference problems (stray currents) are rare. Minimum maintenance required

Disadvantages of galvanic System Limited driving potential Lower current output Can be ineffective in high-resistivity environments

Impressed-current systems employ direct current usually provided by a rectifier attached to an AC power source. The rectifier converts alternating current to direct current. Direct current from the rectifier flows to the buried impressed current anode, from the anode through the soil electrolyte and onto the surface of the steel. The impressed current anodes used in soil are made of materials such as graphite,steel,high silicon cast iron or mixed metal oxides on titanium Advantages of Impressed Current Able to supply a relatively large current capable of protecting large structures Availability of large driving potential Capability of variable current output Applicability to almost any soil resistivity

Disadvantages of Impressed current system. Possible interference problems(stray currents)

Loss of AC power causes loss of protection Higher maintenance and operating cost. Higher cost for small installations More frequent monitoring

Structures that are commonly protected by cathodic protection are the exterior surfaces of: Pipelines Ships hull Storage tank bases Jetties and harbor structures Steel sheet, tubular and foundation pilings Offshore platforms, floating and subsea structures

Cathodic protection is also used to protect the internal surfaces of: Large diameter pipelines Ships tank (product and ballast) Storage tanks (oil and water) Water circulating system Design considerations

Any Substance, when added in small quantities to a corrosive environment containing carbon steel or an alloy that will decrease the corrosion rate is called an inhibitor. Inhibitors function in various ways and are beyond the scope of this manual. Additions of soluble hydroxides, chromates phosphates, silicates and carbonates are used to decrease the corrosion rates of carbon steel and alloys in various corrosive environments. The concentration of a given inhibitor needed to protect a metal will depend on a number of factors such as composition of the environment,temperature,velocity of the liquid, the presence or absence in the metal of internal or external stresses, composition of the metal and the presence of any other metal contact.