CORROSION Corrosion It is the deterioration of a material resulting from chemical attack by its environment.

It usually occurs on metals, ceramics and polymers. Environmental Factors Affecting Corrosion The variables in the corrosion environment include fluid velocity, temperature, composition and mechanical stress can have influence in the corrosion properties of a material. Fluid Velocity enhances the rate of corrosion due to its erosive effects. Increasing Temperature and composition enhances also the reaction rates or chemical reactivity of a material. Corrosion of Metals y It is the destructive and unintentional attack of a metal. It is electrochemical and usually begins at the surface. (e.g., rusting of auto motive body panels). Metals possess free electrons and can set- up electrochemical cells within their structure y On metallic state, energies of metal are higher therefore has a spontaneous tendency to react chemically to form other compounds (e.g., iron oxides-rust)

2H + 2e

H2

Cathode y Site where reduction occurs (Cathodic Reaction) y Note: Both Oxidation and Reduction reactions must occur at the same time and same over all rate to prevent electric charge build up (Thats why, we have Half Reactions) Electrode Potentials y Every metal has a different tendency to corrode in a particular environment (zinc is corroded by H2SO4 ) Galvanic Couple Two metals electrically connected in a liquid electrolyte wherein one becomes an anode and corrodes while the other acts as cathode Standard Hydrogen Electrode It is a reference cell of other cell halves because measured cell voltages represent only differences in electrical potential. Electromotive force series (emf) Generated by coupling SHE standard half cell with various metals, thus ranking them accdg. To voltages Galvanic Series Relative reactivity of metals and commercial alloys in seawater PASSIVITY / PASSIVATION OF METALS Formation of a protective surface layer of reaction product that inhibits further reaction (corrosion- resistant) Loss of chemical reactivity in the presence of a particular environmental condition, thus becoming inert Examples: chromium, nickel, iron, titanium and many of their alloys Two Main Theories of Passive Film 1. OXIDE- FILM THEORY passive film is always a diffusion barrier layer of reaction products thereby separate the metal from the environment and slows down the reaction rate 2. ADSORPTION THEORY passive metals are are covered by chemissorbed films of oxygen Adsorbed H2O molecules are displaced, thereby slowing down the rate of anodic dissolution like the hydration of metals Corrosion of Ceramics

Electrochemical Corrosion of Metals For metallic materials, the corrosion process is normally electrochemical where there is a transfer of electrons from one chemical species to another. OXIDATION metal atoms lose or give up electrons Anode Site were oxidation takes place (Anodic Reaction) Example: Oxidation reaction of metal M M Mn+ + ne2+ Fe Fe + 2e REDUCTION y A metal or non metal is reduced in valence charge y Example: metals undergo corrosion in acid solutions having high + concentrations of H

It is exceedingly immune to corrosion by almost all environmental effects and only simple chemical dissolution occurs. CORROSSION RATE The corrosion rate, or the rate of material removal as a consequence of the chemical action, is an important corrosion parameter. This may be expressed as the corrosion penetration rate (CPR), or the thickness loss of material per unit of time. CPR = KW/rAt W = the weight loss after exposure time t A = exposed specimen area r= density K = constant, its magnitude depending on the system of units used Inasmuch as there is an electric current associated with electrochemical corrosion reactions, we can also express corrosion rate in terms of this current, or, more specifically, current densitythat is, the current per unit surface area of material corrodingwhich is designated i. The rate r, in units of mol/m2-s, is determined using the expression r =i/nf n = number of electrons associated with the ionization of each metal ions. F= 96,500 C/mol. PREDICTION OF CORROSION RATES y Polarization in corrosion refers to any changes in the equilibrium potential of an electrochemical reaction. y The displacement of each electrode potential from its equilibrium value is polarization. y Overvoltage is the magnitude of the displacement, expressed in milivoltage. TWO TYPES OF POLARIZATION 1. Activation Polarization y refers to the condition wherein the reaction rate is controlled by the one step in the series that occurs at the slowest rate y The slowest of these steps determines the rate of the overall reaction. For activation polarization, the relationship between overvoltage and current density i is Ha= (+-) b log i/i0 The reduction of hydrogen ions to form bubbles of hydrogen gas on the surface of a zinc electrode .It is conceivable that this reaction could proceed by the following step sequence:

1. Adsorption of H ions from the solution onto the zinc surface 2. Electron transfer from the zinc to form a hydrogen atom, H+e H 3. Combining of two hydrogen atoms to form a molecule of hydrogen, 2H- H2 4. The coalescence of many hydrogen molecules to form a bubble 2. Concentration Polarization y Exists when the reaction rate is limited by diffusion in the solution. y Concentration polarization data are also normally plotted as overvoltage versus the logarithm of current density. The mathematical expression relating concentration polarization overvoltage and current density i is hc = 2.3RT /nf log a(1 i/iLb) where R and T are the gas constant and absolute temperature, respectively, n and f have the same meanings as above, and iL is the limiting diffusion current density. FORMS OF CORROSION 1. Uniform Attack y A form of electrochemical corrosion that occurs with equivalent intensity over the entire exposed surface and often leaves behind a scale or deposit. y Most common form of corrosion. It is also the least objectionable because it can be predicted and designed for with relative ease. Examples: General rusting of steel and iron Tarnishing of silverware. 2. Galvanic Corrosion y Occurs when two metals or alloys having different compositions are electrically coupled while exposed to an electrolyte. y The less noble or more reactive metal in the particular environment will experience corrosion; the more inert metal, the cathode, will be protected from corrosion. Example: y Steel screws corrode when in contact with brass in a marine environment. y If copper and steel tubing are joined in a domestic water heater, the steel will corrode in the vicinity of the junction.

A number of measures may be taken to significantly reduce the effects of galvanic corrosion. 1. If coupling of dissimilar metals is necessary, choose two that are close together in the galvanic series. 2. Avoid an unfavorable anode-to-cathode surface area ratio; use an anode area as large as possible. 3. Electrically insulate dissimilar metals from each other. 4. Electrically connect a third, anodic metal to the other two; this is a form of cathodic protection. 3. Crevice Corrosion For such a concentration cell, corrosion occurs in the locale that has the lower concentration. A good example of this type of corrosion occurs in crevices and recesses or under deposits of dirt or corrosion products where the solution becomes stagnant and there is localized depletion of dissolved oxygen. Crevice corrosion may be prevented by using welded instead of riveted or bolted joints, using non absorbing gaskets when possible, removing accumulated deposits frequently, and designing containment vessels to avoid stagnant areas and ensure complete drainage.

Erosioncorrosion arises from the combined action of chemical attack and mechanical abrasion or wear as a consequence of fluid motion. y All metal alloys, to one degree or another, are susceptible to erosioncorrosion. y It is especially harmful to alloys that passivate by forming a protective surface film; the abrasive action may erode away the film, leaving exposed a bare metal surface Examples: y Commonly found in piping, especially at bends, elbows, and abrupt changes in pipe diameterpositions where the fluid changes direction or flow suddenly becomes turbulent. y Propellers, turbine blades, valves, and pumps are also susceptible to this form of corrosion. y One of the best ways to reduce erosioncorrosion is to change the design to eliminate fluid turbulence and impingement effects. Other materials may also be utilized that inherently resist erosion. Furthermore, removal of particulates and bubbles from the solution will lessen its ability to erode. 7. Stress Corrosion Stress corrosion, sometimes termed stress corrosion cracking, results from the combined action of an applied tensile stress and a corrosive environment; both influences are necessary. 8. Hydrogen Embrittlement y Various metal alloys, specifically some steels, experience a significant reduction in ductility and tensile strength when atomic hydrogen (H) penetrates into the material. y Hydrogen-induced cracking and hydrogen stress cracking are sometimes also used. y A type of failure; in response to applied or residual tensile stresses, brittle fracture occurs catastrophically as cracks grow and rapidly propagate. Hydrogen embrittlement is similar to stress corrosion in that a normally ductile metal experiences brittle fracture when exposed to both a tensile stress and a corrosive atmosphere Oxidation y It can be thought of as the interaction between oxygen molecules and all the different substances they may contact, from metal to living tissue.

4. Pitting Pitting is another form of very localized corrosion attack in which small pits or holes form. They ordinarily penetrate from the top of a horizontal surface downward in a nearly vertical direction. The mechanism for pitting is probably the same as for crevice corrosion in that oxidation occurs within the pit itself, with complementary reduction at the surface. 5. Intergranular Corrosion y Occurs preferentially along grain boundaries for some alloys and in specific environments. y The net result is that a macroscopic specimen disintegrates along its grain boundaries. y This type of corrosion is especially prevalent in some stainless steels. y It is an especially severe problem in the welding of stainless steels. Often termed weld decay. 6. ErosionCorrosion

Technically, oxidation came to be more precisely defined as the loss of at least one electron when two or more substances interact. Those substances may or may not include oxygen. Sometimes oxidation is not such a bad thing, as in the formation of super-durable anodized aluminum. Other times, oxidation can be destructive, such as the rusting of an automobile or the spoiling of fresh fruit. Oxidation as corrosion mostly happens on an oxidation reaction with oxygen.

y y y

The secret of preventing oxidation caused by oxygen is to provide a layer of protection between the exposed material and the air. This could mean a wax or polyurethane coating on a car, a layer of paint on metal objects or a quick spray of an anti-oxidant. Destructive oxidation cannot occur if the oxygen cannot penetrate a surface to reach the free radicals it craves.

Oxidation and Rust y We often used the words oxidation and rust interchangeably, but not all materials which interact with oxygen molecules actually disintegrate into rust. y In the case of iron, the oxygen creates a slow burning process, which results in the brittle brown substance we call rust. When oxidation occurs in copper, on the other hand, the result is a greenish coating called copper oxide. The metal itself is not weakened by oxidation, but the surface develops a patina after years of exposure to air and water Process of oxidation y When it involves oxygen, the process of oxidation depends on the amount of oxygen present in the air and the nature of the material it touches. y True oxidation happens on a molecular level we only see the large-scale effects as the oxygen causes free radicals on the surface to break away. Oxidation as Corrosion y Oxidation can also be a problem for car owners, since the outermost layers of paint are constantly exposed to air and water. If the car's outer finish is not protected by a wax coating or polyurethane, the oxygen molecules in the air will eventually start interacting with the paint. As the oxygen burns up the free radicals contained in the paint, the finish becomes duller and duller. y Stainless steel doesn't rust and ordinary steel does. The stainless steel has a thin coating of another metal which does not contain free radicals. Regular steel may be painted for protection against oxidation, but oxygen can still exploit any opening, no matter how small. Prevention of Oxidation

CORROSSION PREVENTION y Material selection Perhaps the most common and easiest way of preventing corrosion. Here, cost may be a significant factor. It is not always economically feasible to employ the material that provides the optimum corrosion resistance; sometimes, either another alloy and/or some other measure must be used. y Environmental alteration y Designs y Coatings y cathodic protection ENVIRONMENTAL ALTERATION Changing the character of the environment, if possible, may also significantly influence corrosion. Lowering the fluid temperature and/or velocity usually produces a reduction in the rate at which corrosion occurs. Many times increasing or decreasing the concentration of some species in the solution will have a positive effect; for example, the metal may experience passivation. DESIGNS The design should allow for complete drainage in the case of a shutdown, and easy washing. Since dissolved oxygen may enhance the corrosivity of many solutions, the design should, if possible, include provision for the exclusion of air. INHIBITORS y Substances that, when added in relatively low concentrations to the environment, decrease its corrosiveness. y Specific inhibitor depends both on the alloy and on the corrosive environment. y Some react with and virtually eliminate a chemically active species in the solution (such as dissolved oxygen). y Other inhibitor molecules attach themselves to the corroding surface and interfere with either the oxidation or the reduction reaction, or form a very thin protective coating. y Inhibitors are normally used in closed systems such as automobile radiators and steam boilers.

COATINGS y Physical barriers to corrosion are applied on surfaces in the form of films and coatings. y It is essential that the coating maintain a high degree of surface adhesion, which undoubtedly requires some pre-application surface treatment. y In most cases, the coating must be virtually nonreactive in the corrosive environment and resistant to mechanical damage that exposes the bare metal to the corrosive environment. y All three material typesmetals, ceramics, and polymersare used as coatings for metals. CATHODIC PROTECTION y One of the most effective means of corrosion prevention y It can be used for all eight different forms of corrosion y Completely stop corrosion. y It simply involves supplying, from an external source, electrons to the metal to be protected, making it a cathode. y Cathodic protection is especially useful in preventing corrosion of water heaters, underground tanks and pipes, and marine equipment. CATHODIC PROTECTION TECHNIQUES One cathodic protection technique employs a galvanic couple: the metal to beprotected is electrically connected to another metal that is more reactive in the particular environment. The latter experiences oxidation, and, upon giving up electrons, protects the first metal from corrosion. The oxidized metal is often called a sacrificial anode. Magnesium and zinc are commonly used as such because they lie at the anodic end of the galvanic series. This form of galvanic protection is for structures buried in the ground. For another technique of cathodic protection, the source of electrons is an impressed current from an external dc power source, as represented in (b) for an underground tank. The negative terminal of the power source is connected to the structure to be protected. The other terminal is joined to an inert anode (often graphite), which is, in this case, buried in the soil; high-conductivity backfill material provides good electrical contact between the anode and surrounding soil. Process of galvanizing is simply one in which a layer of zinc is applied to the surface of steel by hot dipping. In the atmosphere and most aqueous environments, zinc is anodic to and will thus cathodically protect the steel if

there is any surface damage .Any corrosion of the zinc coating will proceed at an extremely slow rate because the ratio of the anode-to-cathode surface area is quite large. Degradation of Polymers Swelling partial dissolution process in which there is only limited solubility of the polymer in the solvent Dissolution occurs when the polymer is completely soluble, a continuation of swelling Bond Rupture Scission - the severence or rupture of molecular chain bonds - causes a separation of chain segments at the point of scission and a reduction in the molecular weight - Radiation, Chemical Reaction, Thermal Effects Radiation Effects - certain types of radiation possess sufficient energy to penetrate a polymer specimen and interact the constituent atoms or their electrons Chemical Reaction Effects - oxygen, ozone, and other substances can cause or accelerate chain scission as a result of chemical reaction Thermal Effects - thermal degradation corresponds to the scission of molecular chains at elevated temperatures; as a consequence, some polymers undergo chemical reactions in which gaseous species are produced Weathering - deterioration is the primary result of oxidation, which is initiated by ultraviolet radiation from the sun Summary: Polymers deteriorate by noncorrosive processes. Upon exposure to light, they may experience degradation by swelling or dissolution. With swelling, solute molecules actually fit into the molecular structure. Scission, or the severance of molecular chain bonds, may be induced by radiation, chemical reactions, or heat. This results in a reduction of molecular weight and a deterioration of the physical and chemical properties of the polymer.