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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
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 (That¶s 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
the steel will corrode in the vicinity of the junction. Examples: General rusting of steel and iron Tarnishing of silverware. is determined using the expression r =i/nf n = number of electrons associated with the ionization of each metal ions. y If copper and steel tubing are joined in a domestic water heater. the current per unit surface area of material corroding²which is designated i. y The displacement of each electrode potential from its equilibrium value is polarization.It is conceivable that this reaction could proceed by the following step sequence: 1. more specifically. expressed in milivoltage. or. CPR = KW/rAt W = the weight loss after exposure time t A = exposed specimen area r= density K = constant. 2. respectively. the cathode. Adsorption of H ions from the solution onto the zinc surface 2. or the thickness loss of material per unit of time. This may be expressed as the corrosion penetration rate (CPR). 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. For activation polarization. we can also express corrosion rate in terms of this current. 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. n and f have the same meanings as above.500 C/mol. is an important corrosion parameter. Combining of two hydrogen atoms to form a molecule of hydrogen. its magnitude depending on the system of units used Inasmuch as there is an electric current associated with electrochemical corrosion reactions. y Most common form of corrosion. The rate r. PREDICTION OF CORROSION RATES y Polarization in corrosion refers to any changes in the equilibrium potential of an electrochemical reaction. Galvanic Corrosion y Occurs when two metals or alloys having different compositions are electrically coupled while exposed to an electrolyte. F= 96. the more inert metal. 2H.It is exceedingly immune to corrosion by almost all environmental effects and only simple chemical dissolution occurs. It is also the least objectionable because it can be predicted and designed for with relative ease. The mathematical expression relating concentration polarization overvoltage and current density i is hc = 2. and iL is the limiting diffusion current density.H2 4. H+e H 3. in units of mol/m2-s. CORROSSION RATE The corrosion rate. TWO TYPES OF POLARIZATION 1. 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 . y The less noble or more reactive metal in the particular environment will experience corrosion.3RT /nf log a(1 ±i/iLb) where R and T are the gas constant and absolute temperature. The coalescence of many hydrogen molecules to form a bubble 2. or the rate of material removal as a consequence of the chemical action. will be protected from corrosion. y Concentration polarization data are also normally plotted as overvoltage versus the logarithm of current density. current density²that is. Example: y Steel screws corrode when in contact with brass in a marine environment. FORMS OF CORROSION 1. y Overvoltage is the magnitude of the displacement. Concentration Polarization y Exists when the reaction rate is limited by diffusion in the solution. . Electron transfer from the zinc to form a hydrogen atom.
especially at bends. 5. choose two that are close together in the galvanic series. Crevice Corrosion For such a concentration cell. 4. both influences are necessary. They ordinarily penetrate from the top of a horizontal surface downward in a nearly vertical direction. from metal to living tissue. turbine blades. in response to applied or residual tensile stresses. the abrasive action may erode away the film. are susceptible to erosion±corrosion. and abrupt changes in pipe diameter²positions where the fluid changes direction or flow suddenly becomes turbulent. y It is an especially severe problem in the welding of stainless steels. 3. valves. If coupling of dissimilar metals is necessary. Furthermore. Erosion±corrosion arises from the combined action of chemical attack and mechanical abrasion or wear as a consequence of fluid motion. to one degree or another. removing accumulated deposits frequently. 2. and pumps are also susceptible to this form of corrosion. Crevice corrosion may be prevented by using welded instead of riveted or bolted joints. Hydrogen Embrittlement y Various metal alloys. 1. y It is especially harmful to alloys that passivate by forming a protective surface film. y A type of failure. specifically some steels. The mechanism for pitting is probably the same as for crevice corrosion in that oxidation occurs within the pit itself. y One of the best ways to reduce erosion±corrosion is to change the design to eliminate fluid turbulence and impingement effects.A number of measures may be taken to significantly reduce the effects of galvanic corrosion. 8. corrosion occurs in the locale that has the lower concentration. using non absorbing gaskets when possible. Electrically connect a third. Stress Corrosion Stress corrosion. y This type of corrosion is especially prevalent in some stainless steels. this is a form of cathodic protection. with complementary reduction at the surface. y The net result is that a macroscopic specimen disintegrates along its grain boundaries. y All metal alloys. Intergranular Corrosion y Occurs preferentially along grain boundaries for some alloys and in specific environments. Often termed weld decay. 7. elbows. 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. Avoid an unfavorable anode-to-cathode surface area ratio. and designing containment vessels to avoid stagnant areas and ensure complete drainage. Erosion±Corrosion . 3. 4. use an anode area as large as possible. brittle fracture occurs catastrophically as cracks grow and rapidly propagate. y Propellers. Pitting Pitting is another form of very localized corrosion attack in which small pits or holes form. y Hydrogen-induced cracking and hydrogen stress cracking are sometimes also used. results from the combined action of an applied tensile stress and a corrosive environment. experience a significant reduction in ductility and tensile strength when atomic hydrogen (H) penetrates into the material. removal of particulates and bubbles from the solution will lessen its ability to erode. leaving exposed a bare metal surface Examples: y Commonly found in piping. sometimes termed stress corrosion cracking. Other materials may also be utilized that inherently resist erosion. 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. 6. anodic metal to the other two. Electrically insulate dissimilar metals from each other.
oxidation came to be more precisely defined as the loss of at least one electron when two or more substances interact. include provision for the exclusion of air. if possible. if possible. y Some react with and virtually eliminate a chemically active species in the solution (such as dissolved oxygen). Regular steel may be painted for protection against oxidation. y Environmental alteration y Designs y Coatings y cathodic protection ENVIRONMENTAL ALTERATION Changing the character of the environment. When oxidation occurs in copper. the process of oxidation depends on the amount of oxygen present in the air and the nature of the material it touches. which results in the brittle brown substance we call rust. Oxidation as Corrosion y Oxidation can also be a problem for car owners. y Stainless steel doesn't rust and ordinary steel does. decrease its corrosiveness. sometimes. such as the rusting of an automobile or the spoiling of fresh fruit. INHIBITORS y Substances that. and easy washing. cost may be a significant factor. but oxygen can still exploit any opening.y y y Technically. Destructive oxidation cannot occur if the oxygen cannot penetrate a surface to reach the free radicals it craves. Since dissolved oxygen may enhance the corrosivity of many solutions. no matter how small. Many times increasing or decreasing the concentration of some species in the solution will have a positive effect. If the car's outer finish is not protected by a wax coating or polyurethane. or form a very thin protective coating. a layer of paint on metal objects or a quick spray of an anti-oxidant. Here. Oxidation and Rust y We often used the words oxidation and rust interchangeably. Oxidation as corrosion mostly happens on an oxidation reaction with oxygen. y True oxidation happens on a molecular level ² we only see the large-scale effects as the oxygen causes free radicals on the surface to break away. oxidation can be destructive. . Those substances may or may not include oxygen. This could mean a wax or polyurethane coating on a car. y In the case of iron. the result is a greenish coating called copper oxide. As the oxygen burns up the free radicals contained in the paint. The metal itself is not weakened by oxidation. either another alloy and/or some other measure must be used. Other times. Sometimes oxidation is not such a bad thing. for example. the design should. y Other inhibitor molecules attach themselves to the corroding surface and interfere with either the oxidation or the reduction reaction. the oxygen creates a slow burning process. Lowering the fluid temperature and/or velocity usually produces a reduction in the rate at which corrosion occurs. It is not always economically feasible to employ the material that provides the optimum corrosion resistance. since the outermost layers of paint are constantly exposed to air and water. 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. The stainless steel has a thin coating of another metal which does not contain free radicals. when added in relatively low concentrations to the environment. DESIGNS The design should allow for complete drainage in the case of a shutdown. y Inhibitors are normally used in closed systems such as automobile radiators and steam boilers. the metal may experience passivation. the finish becomes duller and duller. the oxygen molecules in the air will eventually start interacting with the paint. as in the formation of super-durable anodized aluminum. but the surface develops a patina after years of exposure to air and water Process of oxidation y When it involves oxygen. y Specific inhibitor depends both on the alloy and on the corrosive environment. on the other hand. Prevention of Oxidation CORROSSION PREVENTION y Material selection ± Perhaps the most common and easiest way of preventing corrosion. may also significantly influence corrosion. but not all materials which interact with oxygen molecules actually disintegrate into rust.
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. The latter experiences oxidation.certain types of radiation possess sufficient energy to penetrate a polymer specimen and interact the constituent atoms or their electrons Chemical Reaction Effects . the coating must be virtually nonreactive in the corrosive environment and resistant to mechanical damage that exposes the bare metal to the corrosive environment.COATINGS y Physical barriers to corrosion are applied on surfaces in the form of films and coatings. a continuation of swelling Bond Rupture Scission . as a consequence. from an external source.deterioration is the primary result of oxidation. upon giving up electrons. y It simply involves supplying. y All three material types²metals. making it a cathode. For another technique of cathodic protection. y Cathodic protection is especially useful in preventing corrosion of water heaters. electrons to the metal to be protected. underground tanks and pipes. The negative terminal of the power source is connected to the structure to be protected. ceramics.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. Magnesium and zinc are commonly used as such because they lie at the anodic end of the galvanic series. chemical reactions. they may experience degradation by swelling or dissolution. protects the first metal from corrosion. in this case. which is initiated by ultraviolet radiation from the sun Summary: Polymers deteriorate by noncorrosive processes. With swelling. Thermal Effects Radiation Effects .Radiation. The other terminal is joined to an inert anode (often graphite). 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. Upon exposure to light. and polymers²are used as coatings for metals. This form of galvanic protection is for structures buried in the ground. Chemical Reaction. the source of electrons is an impressed current from an external dc power source. or the severance of molecular chain bonds. The oxidized metal is often called a sacrificial anode.the severence or rupture of molecular chain bonds . ozone. or heat. Process of galvanizing is simply one in which a layer of zinc is applied to the surface of steel by hot dipping. and marine equipment. and. zinc is anodic to and will thus cathodically protect the steel if there is any surface damage .oxygen. Scission. This results in a reduction of molecular weight and a deterioration of the physical and chemical properties of the polymer.thermal degradation corresponds to the scission of molecular chains at elevated temperatures. solute molecules actually fit into the molecular structure. In the atmosphere and most aqueous environments. high-conductivity backfill material provides good electrical contact between the anode and surrounding soil. which undoubtedly requires some pre-application surface treatment. and other substances can cause or accelerate chain scission as a result of chemical reaction Thermal Effects . y It is essential that the coating maintain a high degree of surface adhesion.causes a separation of chain segments at the point of scission and a reduction in the molecular weight . . which is. y In most cases. some polymers undergo chemical reactions in which gaseous species are produced Weathering . may be induced by radiation. as represented in (b) for an underground tank. 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. buried in the soil.
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