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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.
Figure 1-1. ∆H 2CaCO3 2CaO + 2CO + O2 The main chemical reaction takes place. such as an oxide. Entropy. and limestone are added to the top of a blast furnace (Figure 1-1). its chemical composition is FE2O3. change toward a condition of maximum probability. . Processed iron ore. An example of this is iron. and additional carbon monoxide. CaO. “Every system which is left to itself will. Fe2O3 + 3CO ∆H 3CO2 + 2Fe The refined iron then runs down and out of the blast furnace to form pig iron. When it is burnt by the hot air it releases both heat energy and the main reducing agent. Metal ore that is mined must be refined and then alloyed for use. 2001). The blast furnace is used to turn iron ore into pig iron for the steel making process.” (G.S.1 The coke is the source of the chemical energy in the blast furnace. Department of Energy's Office of Fossil Energy website (December 14. and the calcium oxide combines with the impurities in the ore to form slag. N. Hematite is a form of iron oxide. CO. Lewis) Energy is required to keep these metals in the refined state and when left alone they will. coke. 2C + O2 ∆H 2CO ∆H = -394 kJ/mol The limestone is decomposed by the heat into calcium oxide. Hematite is the principle ore of iron. drives these metals to corrode. on the average. 1 U. Energy is required to refine these ores into useable metals. The pig iron is then combined with other alloys to get different kinds of steels. a thermodynamic property. over time. revert back to the more stable compounds in which they occur naturally.Thermodynamic and Electrochemical Processes The corrosion process of metals is a natural result of the inherent tendency to revert to a more stable compound.
Fe. • A cathode. is one of the most stable states for iron to be found in. This redox. 4 Allen. Neil T. 10-2. 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. Thomas O. the second law of thermodynamics and free energy come into play.3 It is important to note that when alloys are corroded more than one oxidation and one reduction reaction can occur. • An electrolyte (water) • A metallic path for electron flow. (1986) page 15. When moisture and oxygen are present the iron will undergo a chemical reaction to reduce the amount of free energy available.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. Fe2O3.. in this case the processed iron. which is the state of minimum free energy. has a greater amount of free energy than iron oxide. The second law of thermodynamics quite simply states: “The stable. Roberts. It is important to remember that the anodic and cathodic reactions do not have to occur at the same spot on the material. these halfcells can exist and corrosion will occur.4 Figure 1-2. In this situation four elements are necessary for corrosion to occur: • An anode. . will always be headed towards its most stable state. That energy was added when the ore was heated in the blast furnace. Another way of looking at the corrosion process is as a series of anodic and cathodic reactions. When all four of these elements are present a corrosion cell is formed. The system. Alan P. Fontana. (2001) page 37. equilibrium state of a system is the state of minimum free energy. (1993) page 10-1. reaction produces hydrated iron oxide: 4Fe+2(aq) + O2(g) + [(4 + 2x)H2O](l) [2Fe2O3 · xH2O](s) + 8H+(aq) The resulting iron oxide. 2 3 Davis. Mars G.”2 Iron in the processed form. reduction oxidation. Corrosion cell diagram depicting the current flow from the corrosion pit.
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. Adding chemical inhibitors and coatings to the materials to reduce the current flow will help to increase the circuit resistance. The white areas are where corrosion is most probable. Fe(OH)2. or the possibility exists but there is a tendency for the development of a protective film. Marcel Pourbiax. Pourbiax diagram for an iron-water system at 25û C. It is this series of oxidation and reduction reactions that make up the electrochemistry of the corrosion process. is encountered. The blue zone is where the most stable iron species. 2001). It is the difference in potential between these two sites that causes the electron flow. a well-known Belgian scientist. is stable.The same redox reactions that occurred in the afore mentioned example are occurring in the corrosion cell. Corrosion rates are generally expressed in mils per year of metal thickness reduction (MPY). Figure 1-3 is the Pourbiax diagram for an iron-water system at 25 degrees Celsius. This species is called blue rust and is fairly rare and highly soluble. The flow of electric current in the corrosion cell per unit area is referred to as the Corrosion Current Density (icorr). the non-protective form of corroded iron. 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. developed a diagram which relates the stability of a metal in a given pH environment in 1938. The oxidation reaction takes place at the anode. It is important to note that there is a flow of electrons from one half-cell to the other during the corrosion process. This is the region where the possibility of corrosion is non-existent. The electric current flows from the anodes to the cathodes of the reaction through the electrolyte. and the reduction reaction takes place at the cathode. is expected.6 The gray zone represents the area where the base metal. 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. iron. the possibility for corrosion is non-existent. Corrosion Doctors website (December 13. Figure 1-3. As each oxidation reaction occurs a transfer of electrons to the electrolyte occurs. 5 6 Rohrback Casaco Systems website (December 14.5 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. 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.
This allows for a rate determination for the reactions that are involved in the corrosion process.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.) are referred to as the concentration polarization. in effect a corrosion rate. . The polarization curve is a graph of the variation of the potential as a function of the current. 7 8 Corrosion Doctors website (December 13.8 Figure 1-4. adsorption. 2001). If the potential of the metal surface is polarized by the current in a positive sense it is referred to as being anodically polarized. 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 It is not enough to determine if the possibility for corrosion exists. 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. Corrosion rates are determined through polarization curves. Polarization curves are produced through the application of a current to the metal surface. etc.) are referred to as the activation polarization. a negative sense signifies that it is cathodically polarized. There are software programs available that can produce these diagrams for the student of corrosion processes. Encyclopedia of Electrochemistry website (December 13. The surface process factors (film formation. a corrosion rate must also be determined. dissolved oxygen in the solution. General Polarization curve for a material with both anodic and cathodic polarization curves. etc. It is entirely possible for the probability of corrosion to be high and resultant corrosion rates to be very low. In these cases the corrosion might not be a problem. 2001) page 5.
Passivity generally refers to materials that form insoluble films.. and (c) is controlled by a combination of both reactions. (1995) page 54. icorr.10 These films can markedly reduce the rate of corrosion as long as they are not breached. From this polarization curve the Evans diagram can be extrapolated. . The value of the current at the intersection is the rate of corrosion expressed in current density. or both reactions control the rate of the corrosion. Evans diagram extrapolated from the polarization curve (a) shows that the rate is controlled by the anodic reaction.The polarization curve above shows the polarization curves for both anodic and cathodic reactions. cathodic. which can be controlled. (b) is controlled by the cathodic reaction. (b) is controlled by the cathodic reaction. is plotted as a function of the logarithm of icorr. Atkinson. The potential.N. on the rates of corrosion. is determined by the intersection of the extrapolation of the linear portions of the anodic and cathodic polarization curves. Another determining factor in the corrosion rate is the phenomenon of passivity and passive films.T. Evans diagrams are useful in determining if the anodic. and (c) is controlled by a combination of both reactions. (a) shows that the rate is controlled by the anodic reaction. which inhibit the anodic reactions and cause a polarization of the anode. Ecorr. the corrosion potential. Van Droffelaar. E. Figure 1-5 shows the three types of Evans diagrams that can be extrapolated from the polarization curve. which is readily available in nature. One of the major causes of the breaching of the passive films is the chloride ion. These films can experience breakdowns from both electrochemical reactions and mechanical mechanisms. 2001) page 6. 9 10 Encyclopedia of Electrochemistry website (December 13. J. This information is used by corrosion engineers to allow the evaluation of the effects of measurable factors. H. Those discrete sites where a breach in the film occurs can experience an accelerated rate of corrosion.9 Figure 1-5.
Making the material thicker than necessary to accommodate the corrosion throughout the life of the product. 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. General corrosion occurs uniformly over the entire surface that is exposed. Depicts general. It is fairly consistent and rates can quickly be found by exposing a sample to the environment. 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.An interesting process that some alloys undergo is repassivation. . 11 Encyclopedia of Electrochemistry website (December 13. or uniform. corrosion on a steel fitting. which are significantly different from one another. such as paint. General Corrosion General corrosion. This form of corrosion is generally the cheapest form of corrosion to deal with in industry. • Stress corrosion: generally cracking that is induced by environmental factors. or uniform attack. 2001) page 6. • Metallurgically Induced corrosion • Mechanically Assisted corrosion: physical environmental factors play a significant role in metal loss. This process is very effective for combating localized corrosion. • Uniform or General corrosion: a regular loss of metal from the surface cases a uniform thinning. The metal gets thinner evenly over the entire surface. 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. leading this form of corrosion to account for the largest tonnage of metal loss. These five basic types of corrosion can be broken down into eight visually identifiable forms. Photo 2-1. is the most common form of corrosion.11 Forms of Corrosion From the engineers standpoint the forms that corrosion takes can generally be identified by a visual examination. or applying a coating to the surface. These alloys form a passive film that resists the breakdown process in a fairly effective manor. • Localized corrosion: the majority of metal loss is experienced in discrete areas. are the standard methods of prevention for this form of corrosion.
Light galvanic corrosion around a bolt on a pump housing.Galvanic Corrosion Galvanic. The Galvanic Scale. While the less corrosion resistant metal becomes the anode. The ensuing corrosion reaction is a perfect example of the corrosion cell in figure 1-2. either through direct contact or an electrolyte. or two-metal. Galvanic corrosion of a bolt. or noble. . Photo 2-6. metal becomes the cathode and experiences very little. Photo 2-5. The corrosion resistant. When these two metals can be connected electrically. corrosion occurs because of the potential difference that exists between two dissimilar metals. Figure 2-1. if any metal loss. the difference in potential causes a flow of electrons. between them. or current. 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.
It generally occurs in cracks. (1982) page 47. 12 Dillon. . and anywhere else that small amounts of solution can lay stagnate. As the oxygen is depleted the growth of the corrosion cell is driven by the accumulation of acidic hydrolyzed salts in the crevice area. an oxygen concentration cell. and fasteners of the same material or a more noble material should be used.Proper material selection can eliminate most of the problems associated with galvanic corrosion. Photo 2-9. Combinations of metals and alloys used together should not be widely separated on the galvanic scale. Crevice Corrosion Crevice corrosion is an intensive. holes. Crevice corrosion begins with the typical corrosion cell (figure 1-2).P. rivet and bolt heads. Galvanic corrosion at the threaded connection between a brass fitting and a steel backwash line for a water softener. lap joints. should be avoided. Failure due to crevice corrosion in the threaded area of a pipe. Photo 2-8. such as threaded connections. Corrosion of a brass fitting due to the galvanic couple created with the copper pipe. Dissimilar metal crevices. under gaskets.12 Photo 2-7. C. crevices. localized form of corrosion.
Photo 2-11. and the corrosion of the bolts that held the flange together. . Notice the extensive corrosion between the flange faces. Crevice corrosion is very common in tube and shell heat exchangers.Photo 2-10. Photo courtesy Tim Milanowski. The main areas of concern are where the tubes enter the tube sheets and where they go through the baffles. Excellent example of crevice corrosion on several fronts. 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 2-12. Notice that the pitting occurs on the bottom half of the pipe. This is an oily water line. C. 13 Dillon. that experienced failure due to pitting.P. Photo 2-13. Pits usually grow in the direction of gravity. (1982) page 19. Pitting is an extremely localized form of attack that often causes rapid penetration of the wall thickness. and the glycol tracing that was welded to it. The largest pits and the failure occurred in the heat-affected zone where the glycol heat trace was welded to the pipe. this pit had penetrated about 90% of the way through the wall.Pitting Pitting is a troublesome form of corrosion. 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. It can cause a failure with very little metal loss.13 The holes that pitting causes can be very small or quite large in diameter. Large pit that occurred in an oily water line. .
The preferential attack along the grain boundaries can lead to a decrease in effective cross section of material and eventual mechanical failure. and 2-16 show how varied small pits can be. C. Photos 2-14. Photo 2-17. Material selection. quenching. heat-treating. . 2-15.P. Wormhole pit in a 1-inch diameter steel water pipe. This is a case of weld decay in the heat-affected zone. Failure caused by a small pit. Sensitizing usually occurs through damaging thermal exposures. Photo 2-16 (left). Intergranular Corrosion Intergranular corrosion is the corrosion of the edges of the individual grains that make up the metal. Hole in oily water line caused by pitting. In order to detect that there is a problem you would have to use UT. (1982) page 89. 14 Dillon. Photo 2-15 (upper right). such as welding.14 Metals experiencing intergranular corrosion that should otherwise exhibit excellent corrosion resistant tendencies have been sensitized. and be lucky enough to be right on top of the pit. and proper welding techniques are effective methods for avoiding intergranular corrosion.Photo 2-14 (upper left). This is the heat-affected zone from photo 2-13.
Photo 2-21 and Photo 2-22. Dezincification of a brass valve. or zinc oxide builds up on the outside of the brass piece. Heat-affected zone of a circumferential weld is very distinct in this photo.Photo 2-18. Carburization. . is the removal of one element from an alloy through a corrosion process. The most common form of dealloying is the removal of zinc from brass alloys. Photo 2-19 and 2-20. a special case of intergranular corrosion. This steel hook has undergone carburization at high temperatures. or dealloying. Selective Leaching Selective leaching. Common yellow brass is 30% zinc and 70% copper. The brass turns a red or copper color that contrasts with the original yellow brass.
Here is a good case of two forms of corrosion working together. In order for the flow meter to work properly the diameter of the pipe was reduced several feet upstream of the meter. This is from a section of piping just downstream of a flow meter. Photo courtesy Tim Milanowski. Photo 2-24. Photo 2-23. but it is obvious that erosion played the bigger part in creating the hole itself.Erosion Corrosion Erosion corrosion is the accelerated increase in deterioration of a metal due to the velocity of the fluid. they are deeper on the downstream side (above the weld line). Photo courtesy Tim Milanowski. The velocity effects of the shell side fluid in the tube and shell exchanger are quite obvious. Hole in the HAZ. The failure is actually in the heat-affected zone of the weld. but the metal will be worn away faster if there are abrasives present. The fluid does not have to contain any abrasive particles. . This reduction in diameter increased the velocity through the section of pipe. This failure was caused by erosion corrosion. Notice the shape of the pits.
This photo illustrates unique patterns that occur in some of the erosion corrosion cases. Photo 2-27. Photo courtesy Tim Milanowski.Photo 2-25. Photo courtesy Tim Milanowski. Severe erosion corrosion around a nozzle in a tube and shell heat exchanger. . Severe erosion corrosion due to impingement in a tube and shell heat exchanger. Photo 2-26.
Summary Through a visual examination it is often possible to classify a corrosion problem by the forms of corrosion that are present. The tensile stresses can come from applied stresses or residual stresses. welding. Photo 2-29. Residual stresses are introduced into a material through forming. These two pieces are from the same sump as photo 2-28. More Chloride induced stress corrosion cracking. while fine cracks progress through it. Photo 2-28.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. heat treatments. which is where the ring would experience the greatest stresses. The cracks are at right angles to the setscrew. and grinding. The type of corrosion present tells a lot about the corrosion mechanisms involved and possible methods to control or alleviate the . machining. This is part of a sump float that exhibits signs of chloride induced stress corrosion cracking.
Photo by Tim Milanowski. • Pitting. and will they work together? The Last Exchange. . Through a careful analysis of the problem a method to avoid any similar problems in the future can be found. • Galvanic Corrosion.corrosion problem. • Intergranular Corrosion. Corrosion can usually be placed in to one or more of the following visual forms: • General or Uniform Corrosion. • Erosion Corrosion. • Stress Corrosion Cracking. • Selective Leeching. The most important part of any design from the corrosion standpoint is: Are the materials chosen the right materials for the job. • Crevice Corrosion.
Thomas O.cems. Van Droffelaar. 2001) http://www.com/cs/corrosion1/index.E. Davis.htm.kcs. D. Texas). Alan P. Korb. and Harde. Allen. (1986) Corrosion Engineering (McGraw-Hill. Inc.alyeskapipe. 2001) http://www3. 2001) http://www. Seager. 2001) http://corrosion. C.com/pipelinefacts. Atkinson.com Chemistry website (December 4..com. (1982) Forms of Corrosion Recognition and Prevention (NACE International: Houston.edu/ed/encycl/. Lawrence J.N. (2001) Permafrost A Guide To Frozen Ground in Transition (University of Alaska Press)... (1999) Cold Climate Corrosion Special Topics: Thermodynamic Consideration Relevant to Corrosion of Pipeline Steels in Permafrost (NACE International: New York. Olson. Neil T.htm. (1999) Cold Climate Corrosion Special Topics: Telluric Current Effects on Long and Short Pipelines (NACE International: New York.about.References: About.H. New York) pp 37-66.P.umn. Corrosion Doctors website (December 13. Encyclopedia of Electrochemistry website (December 13. (1995) Corrosion and Its Control (NACE International: Houston. C. Corrosion Research Center website (December 1. David L.org. R. Dillon. (1993) Productions Operations Volume 2 (Oil & Gas Consultants International. Oklahoma). Texas). C. J.edu/research/crc/. Mars G. Corrosion Source website (December 4. White.. 2001) http://www.J. (1987) Metals Handbook Ninth Edition.cwru. H. W. .gov/html/crevcor. 2001) http://chemengineer. Boteler.corrosionsource. Corrosion Technology Testbed website (December 11. 2001) http://electrochem.T. Roberts. Fontana. Texas). W..html.: Tulsa. King.. Inc: New York.nasa. New York).. Volume 13 Corrosion (ASM International: Houston.corrosion-doctors. Alyeska Pipeline Company website (December 12.H. Johanson. New York) pp 67-79.
Minnesota Power Electric website (December 12.edu/users/r/c/rcw134/crevice. 2001) http://www. The Hendrix Group website (December 4.com/tidbits.com/storms/elctrjet.mpelectric. B.html.lanl.Milanowski.psu.com/rcs/. Department of Energy’s Office of Fossil Energy website (December 10. Southwest Research Institute website (December 13. Ryan’s Crevice Corrosion Page (December 10. 2001) http://www. 2001) http://www.html. 2001) http://www. Rohrback Casasco Systems website (December 14. Moniz. (1994) Metallurgy (American Technical Publishers. Tim (December 2001) Inspection Coordinator for Williams Alaska Petroleum.htm.: Homewood. U.swri. .personal. 2001) http://www. 2001) http://www. Alaska. Illinois).corrpro.J.gov/projects/cctc/factsheets/bstel/blastfgrandemo.org/3pubs/ttoday/fall96/pipe.html. North Pole.S.hghouston. Inc.htm.