The 8 Forms of Corrosion

M.E. 464 Brett A. Anderson December 20, 2001

Corrosion is a costly and potentially life threatening problem in any industry. Wherever there is metal the potential for a corrosive reaction exists. It is a natural part of nature, there is no escaping it. That doesn’t mean that we are doomed though. Through a careful analysis of the process and the design we can mitigate most of the costs of corrosion, both actual and potential, before the first pipe is in place. The science of corrosion engineering is viewed by many as magic, or art, but once the basics of how a corrosion cell works and a little understanding of chemistry almost anyone can learn to decipher the clues to the causes of a corrosion problem. Most corrosion problems encountered fall into five basic categories: • Uniform or general corrosion: this is the most common form of corrosion encountered. • Localized corrosion: as the name implies this form of corrosion occurs in discreet areas on the surface of the metal. • Metallurgically induced corrosion: this form of corrosion attacks the metal’s physical and chemical makeup. • Mechanically assisted corrosion: the physical parameters of the system play an important part in this form of corrosion. • Stress corrosion cracking: this form of corrosion results in cracks in the metal that are induced by both stresses and corrosive elements. With this information we can hopefully reduce the costs of replacing expensive assets before they have fully depreciated, but our ultimate goal is to reduce the chances of a catastrophic failure or loss of life due to a corroded system.

change toward a condition of maximum probability. Department of Energy's Office of Fossil Energy website (December 14. coke. on the average. a thermodynamic property. its chemical composition is FE2O3. An example of this is iron. 2C + O2 ∆H 2CO ∆H = -394 kJ/mol The limestone is decomposed by the heat into calcium oxide. Processed iron ore. revert back to the more stable compounds in which they occur naturally. “Every system which is left to itself will. such as an oxide. CaO. 2001).Thermodynamic and Electrochemical Processes The corrosion process of metals is a natural result of the inherent tendency to revert to a more stable compound. Lewis) Energy is required to keep these metals in the refined state and when left alone they will.” (G. When it is burnt by the hot air it releases both heat energy and the main reducing agent. Figure 1-1. over time. . and additional carbon monoxide. Entropy. 1 U. The blast furnace is used to turn iron ore into pig iron for the steel making process.S. N. ∆H 2CaCO3 2CaO + 2CO + O2 The main chemical reaction takes place. CO.1 The coke is the source of the chemical energy in the blast furnace. Fe2O3 + 3CO ∆H 3CO2 + 2Fe The refined iron then runs down and out of the blast furnace to form pig iron. and limestone are added to the top of a blast furnace (Figure 1-1). The pig iron is then combined with other alloys to get different kinds of steels. Metal ore that is mined must be refined and then alloyed for use. drives these metals to corrode. Hematite is a form of iron oxide. and the calcium oxide combines with the impurities in the ore to form slag. Hematite is the principle ore of iron. Energy is required to refine these ores into useable metals.

(1993) page 10-1. The second law of thermodynamics quite simply states: “The stable.4 Figure 1-2. As long as an electrolyte and a metallic path exist. Figure 1-2 is an example of the corrosion cell with the four elements labeled. Roberts. It is important to remember that the anodic and cathodic reactions do not have to occur at the same spot on the material. When moisture and oxygen are present the iron will undergo a chemical reaction to reduce the amount of free energy available. In this situation four elements are necessary for corrosion to occur: • An anode. Mars G. (2001) page 37. will always be headed towards its most stable state. Thomas O. Neil T. . equilibrium state of a system is the state of minimum free energy.”2 Iron in the processed form.At this point. This simple example of an electrochemical reaction demonstrates one of the most important principles of metallic corrosion: the rate of oxidation equals the rate of reduction. is one of the most stable states for iron to be found in. Another way of looking at the corrosion process is as a series of anodic and cathodic reactions. 2 3 Davis.3 It is important to note that when alloys are corroded more than one oxidation and one reduction reaction can occur. That energy was added when the ore was heated in the blast furnace. This redox. • A cathode. 4 Allen. reaction produces hydrated iron oxide: 4Fe+2(aq) + O2(g) + [(4 + 2x)H2O](l) [2Fe2O3 · xH2O](s) + 8H+(aq) The resulting iron oxide. Fe2O3. 10-2. Fontana. these halfcells can exist and corrosion will occur. which is the state of minimum free energy. The system. has a greater amount of free energy than iron oxide. When all four of these elements are present a corrosion cell is formed. reduction oxidation. in this case the processed iron.. (1986) page 15. Alan P. • An electrolyte (water) • A metallic path for electron flow. Corrosion cell diagram depicting the current flow from the corrosion pit. the second law of thermodynamics and free energy come into play. Fe.

As each oxidation reaction occurs a transfer of electrons to the electrolyte occurs. Fe(OH)2. 2001). a well-known Belgian scientist. is stable. The free energy available in the metal and in the electrolyte creates a potential at the anode and at the cathode. The orange zone is where rust. Adding chemical inhibitors and coatings to the materials to reduce the current flow will help to increase the circuit resistance. This is the region where the possibility of corrosion is non-existent. developed a diagram which relates the stability of a metal in a given pH environment in 1938. By plotting the potential of a metal and the pH of the environment it is possible to determine if the metal is in a region where the possibility of corrosion is high. Corrosion rates are generally expressed in mils per year of metal thickness reduction (MPY). the non-protective form of corroded iron. or the possibility exists but there is a tendency for the development of a protective film. Figure 1-3 is the Pourbiax diagram for an iron-water system at 25 degrees Celsius. Since icorr is a measure of current flow per unit area per unit time it can be seen that icorr can be related to units of metal loss per unit time. It is this series of oxidation and reduction reactions that make up the electrochemistry of the corrosion process. This species is called blue rust and is fairly rare and highly soluble. Corrosion Doctors website (December 13.6 The gray zone represents the area where the base metal. It is important to note that there is a flow of electrons from one half-cell to the other during the corrosion process. so icorr is a good representative of the corrosion rate in the cell. 2001) page 3. Most corrosion reactions are considered wet and occur in the presence of a liquid.The same redox reactions that occurred in the afore mentioned example are occurring in the corrosion cell. iron. the possibility for corrosion is non-existent. The blue zone is where the most stable iron species. Pourbiax diagram for an iron-water system at 25û C. The electric current flows from the anodes to the cathodes of the reaction through the electrolyte.5 Armed with this information it is possible to slow down or even prevent the corrosion from occurring by increasing the resistance in the electrochemical corrosion circuit. The flow of electric current in the corrosion cell per unit area is referred to as the Corrosion Current Density (icorr). The oxidation reaction takes place at the anode. The white areas are where corrosion is most probable. is expected. 5 6 Rohrback Casaco Systems website (December 14. It is the difference in potential between these two sites that causes the electron flow. is encountered. Figure 1-3. and the reduction reaction takes place at the cathode. Marcel Pourbiax. .

Encyclopedia of Electrochemistry website (December 13. The surface process factors (film formation.) are referred to as the activation polarization.7 It is not enough to determine if the possibility for corrosion exists. Corrosion rates are determined through polarization curves. which allows the effects of the concentration and activation processes on the rate at which the anodic or cathodic reactions can give or receive electrons to be determined. The environmental factors (the concentrations of metal ions. adsorption. in effect a corrosion rate. 2001). a corrosion rate must also be determined. Polarization curves are produced through the application of a current to the metal surface. The polarization curve is a graph of the variation of the potential as a function of the current.) are referred to as the concentration polarization. If the potential of the metal surface is polarized by the current in a positive sense it is referred to as being anodically polarized.These Pourbiax diagrams are time consuming to create and a new diagram must be created for each metal or alloy that is being used and the environment it is in. 2001) page 5. dissolved oxygen in the solution. a negative sense signifies that it is cathodically polarized. General Polarization curve for a material with both anodic and cathodic polarization curves.8 Figure 1-4. etc. The degree of polarization is a measure of how the rates of the anodic and cathodic reactions are hindered by various environmental and surface process factors. 7 8 Corrosion Doctors website (December 13. There are software programs available that can produce these diagrams for the student of corrosion processes. It is entirely possible for the probability of corrosion to be high and resultant corrosion rates to be very low. This allows for a rate determination for the reactions that are involved in the corrosion process. . In these cases the corrosion might not be a problem. etc.

Ecorr. Evans diagram extrapolated from the polarization curve (a) shows that the rate is controlled by the anodic reaction. Evans diagrams are useful in determining if the anodic. Another determining factor in the corrosion rate is the phenomenon of passivity and passive films. (a) shows that the rate is controlled by the anodic reaction. on the rates of corrosion. . the corrosion potential. From this polarization curve the Evans diagram can be extrapolated. and (c) is controlled by a combination of both reactions. One of the major causes of the breaching of the passive films is the chloride ion. The value of the current at the intersection is the rate of corrosion expressed in current density. and (c) is controlled by a combination of both reactions. cathodic. This information is used by corrosion engineers to allow the evaluation of the effects of measurable factors. Those discrete sites where a breach in the film occurs can experience an accelerated rate of corrosion. E.N.. Figure 1-5 shows the three types of Evans diagrams that can be extrapolated from the polarization curve. icorr. which is readily available in nature.T. 9 10 Encyclopedia of Electrochemistry website (December 13. is determined by the intersection of the extrapolation of the linear portions of the anodic and cathodic polarization curves.10 These films can markedly reduce the rate of corrosion as long as they are not breached. or both reactions control the rate of the corrosion. 2001) page 6. Van Droffelaar. Atkinson. which can be controlled.9 Figure 1-5. These films can experience breakdowns from both electrochemical reactions and mechanical mechanisms. which inhibit the anodic reactions and cause a polarization of the anode.The polarization curve above shows the polarization curves for both anodic and cathodic reactions. (b) is controlled by the cathodic reaction. The potential. J. H. is plotted as a function of the logarithm of icorr. (1995) page 54. Passivity generally refers to materials that form insoluble films. (b) is controlled by the cathodic reaction.

such as paint. It is fairly consistent and rates can quickly be found by exposing a sample to the environment. This process is very effective for combating localized corrosion. This form of corrosion is generally the cheapest form of corrosion to deal with in industry. or uniform. leading this form of corrosion to account for the largest tonnage of metal loss. corrosion on a steel fitting. These five basic types of corrosion can be broken down into eight visually identifiable forms. • Metallurgically Induced corrosion • Mechanically Assisted corrosion: physical environmental factors play a significant role in metal loss. 11 Encyclopedia of Electrochemistry website (December 13.An interesting process that some alloys undergo is repassivation. Making the material thicker than necessary to accommodate the corrosion throughout the life of the product. or applying a coating to the surface. The metal gets thinner evenly over the entire surface. is the most common form of corrosion. 2001) page 6. Depicts general. and are capable of repassivating at a rate high enough that once a breach has occurred the exposure to the corrosive environment is reduced to a minimum.11 Forms of Corrosion From the engineers standpoint the forms that corrosion takes can generally be identified by a visual examination. Photo 2-1. It is usually possible to determine a probable mechanism for the corrosion by corresponding the corrosion in question to one or more of general forms. • Uniform or General corrosion: a regular loss of metal from the surface cases a uniform thinning. This allows an engineer to examine a specimen and make a reasonable assumption on the general cause of the corrosion and possible corrective measures that can be taken. • Stress corrosion: generally cracking that is induced by environmental factors. or uniform attack. are the standard methods of prevention for this form of corrosion. These alloys form a passive film that resists the breakdown process in a fairly effective manor. General Corrosion General corrosion. General corrosion occurs uniformly over the entire surface that is exposed. • Localized corrosion: the majority of metal loss is experienced in discrete areas. . which are significantly different from one another.

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or current. Light galvanic corrosion around a bolt on a pump housing. . if any metal loss. metal becomes the cathode and experiences very little. Photo 2-5.Galvanic Corrosion Galvanic. The corrosion resistant. between them. The further apart on the Galvanic Scale (figure 2-1) that these two metals are increases the amount of corrosion experienced by anodic member of the galvanic couple. Photo 2-6. When these two metals can be connected electrically. either through direct contact or an electrolyte. Galvanic corrosion of a bolt. or two-metal. The ensuing corrosion reaction is a perfect example of the corrosion cell in figure 1-2. the difference in potential causes a flow of electrons. Figure 2-1. The Galvanic Scale. corrosion occurs because of the potential difference that exists between two dissimilar metals. or noble. While the less corrosion resistant metal becomes the anode.

holes. and fasteners of the same material or a more noble material should be used. Photo 2-9.12 Photo 2-7. It generally occurs in cracks. . Dissimilar metal crevices.P. Corrosion of a brass fitting due to the galvanic couple created with the copper pipe. (1982) page 47. Crevice Corrosion Crevice corrosion is an intensive. crevices. Crevice corrosion begins with the typical corrosion cell (figure 1-2). Combinations of metals and alloys used together should not be widely separated on the galvanic scale. C. and anywhere else that small amounts of solution can lay stagnate. an oxygen concentration cell. Photo 2-8. lap joints. Galvanic corrosion at the threaded connection between a brass fitting and a steel backwash line for a water softener. should be avoided. rivet and bolt heads. such as threaded connections. under gaskets. As the oxygen is depleted the growth of the corrosion cell is driven by the accumulation of acidic hydrolyzed salts in the crevice area. Failure due to crevice corrosion in the threaded area of a pipe. 12 Dillon. localized form of corrosion.Proper material selection can eliminate most of the problems associated with galvanic corrosion.

Proper material selection and design features that limit the number of crevices and allow for drainage are the most effective way of mitigating the effects of crevice corrosion. Photo 2-11. Excellent example of crevice corrosion on several fronts. The main areas of concern are where the tubes enter the tube sheets and where they go through the baffles.Photo 2-10. Crevice corrosion is very common in tube and shell heat exchangers. . and the corrosion of the bolts that held the flange together. Photo courtesy Tim Milanowski. Notice the extensive corrosion between the flange faces.

It can cause a failure with very little metal loss. C. The fact that failure can occur with very little metal loss and with just one little area affected is what makes this form of corrosion so difficult to detect and prevent. Photo 2-13. Photo 2-12. This is an oily water line.P. this pit had penetrated about 90% of the way through the wall. that experienced failure due to pitting. Pits usually grow in the direction of gravity. Large pit that occurred in an oily water line. and the glycol tracing that was welded to it. Pitting is an extremely localized form of attack that often causes rapid penetration of the wall thickness.Pitting Pitting is a troublesome form of corrosion. Notice that the pitting occurs on the bottom half of the pipe. 13 Dillon. .13 The holes that pitting causes can be very small or quite large in diameter. The largest pits and the failure occurred in the heat-affected zone where the glycol heat trace was welded to the pipe. (1982) page 19.

and proper welding techniques are effective methods for avoiding intergranular corrosion. Photo 2-16 (left). such as welding. heat-treating.14 Metals experiencing intergranular corrosion that should otherwise exhibit excellent corrosion resistant tendencies have been sensitized. The preferential attack along the grain boundaries can lead to a decrease in effective cross section of material and eventual mechanical failure. Hole in oily water line caused by pitting.Photo 2-14 (upper left). and be lucky enough to be right on top of the pit. Failure caused by a small pit. Material selection. Intergranular Corrosion Intergranular corrosion is the corrosion of the edges of the individual grains that make up the metal. quenching. Photo 2-15 (upper right). . This is a case of weld decay in the heat-affected zone. C. In order to detect that there is a problem you would have to use UT. 14 Dillon. and 2-16 show how varied small pits can be. (1982) page 89. This is the heat-affected zone from photo 2-13.P. Photo 2-17. Wormhole pit in a 1-inch diameter steel water pipe. Sensitizing usually occurs through damaging thermal exposures. 2-15. Photos 2-14.

Selective Leaching Selective leaching. a special case of intergranular corrosion. Heat-affected zone of a circumferential weld is very distinct in this photo. Common yellow brass is 30% zinc and 70% copper. . or dealloying.Photo 2-18. Photo 2-21 and Photo 2-22. The most common form of dealloying is the removal of zinc from brass alloys. Photo 2-19 and 2-20. The brass turns a red or copper color that contrasts with the original yellow brass. Carburization. is the removal of one element from an alloy through a corrosion process. Dezincification of a brass valve. This steel hook has undergone carburization at high temperatures. or zinc oxide builds up on the outside of the brass piece.

This failure was caused by erosion corrosion. This is from a section of piping just downstream of a flow meter. Photo courtesy Tim Milanowski. they are deeper on the downstream side (above the weld line). Photo 2-24. The failure is actually in the heat-affected zone of the weld. The fluid does not have to contain any abrasive particles. Here is a good case of two forms of corrosion working together. This reduction in diameter increased the velocity through the section of pipe.Erosion Corrosion Erosion corrosion is the accelerated increase in deterioration of a metal due to the velocity of the fluid. Photo courtesy Tim Milanowski. In order for the flow meter to work properly the diameter of the pipe was reduced several feet upstream of the meter. The velocity effects of the shell side fluid in the tube and shell exchanger are quite obvious. Notice the shape of the pits. Photo 2-23. but it is obvious that erosion played the bigger part in creating the hole itself. . Hole in the HAZ. but the metal will be worn away faster if there are abrasives present.

Photo 2-25. Photo 2-27. Severe erosion corrosion around a nozzle in a tube and shell heat exchanger. Photo courtesy Tim Milanowski. Photo courtesy Tim Milanowski. Photo 2-26. Severe erosion corrosion due to impingement in a tube and shell heat exchanger. This photo illustrates unique patterns that occur in some of the erosion corrosion cases. .

Photo 2-29. The tensile stresses can come from applied stresses or residual stresses. The cracks are at right angles to the setscrew. These two pieces are from the same sump as photo 2-28. welding. heat treatments. while fine cracks progress through it. Summary Through a visual examination it is often possible to classify a corrosion problem by the forms of corrosion that are present. which is where the ring would experience the greatest stresses. The type of corrosion present tells a lot about the corrosion mechanisms involved and possible methods to control or alleviate the . Photo 2-28. Residual stresses are introduced into a material through forming. machining. More Chloride induced stress corrosion cracking.Stress Corrosion Cracking Stress corrosion cracking (SCC) is the cracking from a combined presence of tensile stresses and a corrosive medium. The metal remains unattacked over its surface. This is part of a sump float that exhibits signs of chloride induced stress corrosion cracking. and grinding.

• Intergranular Corrosion. • Selective Leeching. . Photo by Tim Milanowski. Through a careful analysis of the problem a method to avoid any similar problems in the future can be found.corrosion problem. Corrosion can usually be placed in to one or more of the following visual forms: • General or Uniform Corrosion. and will they work together? The Last Exchange. • Crevice Corrosion. • Galvanic Corrosion. • Pitting. • Stress Corrosion Cracking. The most important part of any design from the corrosion standpoint is: Are the materials chosen the right materials for the job. • Erosion Corrosion.

alyeskapipe.nasa.. Encyclopedia of Electrochemistry website (December 13. Roberts.kcs. New York) pp 37-66.. 2001) http://www.com Chemistry website (December 4. (1995) Corrosion and Its Control (NACE International: Houston. Alyeska Pipeline Company website (December 12. Johanson. Mars G. Inc.cwru. (1987) Metals Handbook Ninth Edition.edu/research/crc/. New York). King. Seager.N.com/pipelinefacts. (2001) Permafrost A Guide To Frozen Ground in Transition (University of Alaska Press). Allen. 2001) http://corrosion. Davis. D. W. Alan P.. Corrosion Research Center website (December 1.corrosion-doctors. (1986) Corrosion Engineering (McGraw-Hill.umn..: Tulsa. H. Corrosion Source website (December 4.. W. J. . Dillon. 2001) http://chemengineer.H.P. 2001) http://electrochem. Volume 13 Corrosion (ASM International: Houston. C.org. Inc: New York. (1999) Cold Climate Corrosion Special Topics: Thermodynamic Consideration Relevant to Corrosion of Pipeline Steels in Permafrost (NACE International: New York. Neil T. Thomas O.. (1999) Cold Climate Corrosion Special Topics: Telluric Current Effects on Long and Short Pipelines (NACE International: New York.com. Oklahoma). (1982) Forms of Corrosion Recognition and Prevention (NACE International: Houston. New York) pp 67-79.htm. Texas).corrosionsource. Corrosion Technology Testbed website (December 11. Fontana.htm. C. C. David L. 2001) http://www.gov/html/crevcor. (1993) Productions Operations Volume 2 (Oil & Gas Consultants International. Van Droffelaar.about.H. Texas). Texas). and Harde.References: About.J.com/cs/corrosion1/index.cems. Corrosion Doctors website (December 13.html. R. White. Korb. Boteler. 2001) http://www3.E.T. Lawrence J. Olson. Atkinson. 2001) http://www..edu/ed/encycl/.

html. Alaska.com/rcs/. Tim (December 2001) Inspection Coordinator for Williams Alaska Petroleum. Southwest Research Institute website (December 13. 2001) http://www. Inc.swri.com/storms/elctrjet. Minnesota Power Electric website (December 12.html. B. Moniz.personal.htm. Illinois). Ryan’s Crevice Corrosion Page (December 10.S. The Hendrix Group website (December 4. 2001) http://www.htm. North Pole. 2001) http://www.lanl.com/tidbits.hghouston. Rohrback Casasco Systems website (December 14.org/3pubs/ttoday/fall96/pipe.: Homewood. U.html.gov/projects/cctc/factsheets/bstel/blastfgrandemo.corrpro.J. (1994) Metallurgy (American Technical Publishers. 2001) http://www. . 2001) http://www.Milanowski.edu/users/r/c/rcw134/crevice.mpelectric.psu. Department of Energy’s Office of Fossil Energy website (December 10. 2001) http://www.

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