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Corrosion and Protection Centre

Module 0 – Introduction to Corrosion

Module Notes - Localized Corrosion

September 2003

All rights reserved . the Corrosion and Protection Centre.This document is © 2002 .2003. UMIST.

such as the presence of second phase precipitates. Localized Corrosion . and fluctuating stress. by inherent variations in the structure or composition of the metal. and fails at local points. Since the rate of corrosion processes is often controlled by the rate of supply of oxygen to the metal surface. oxygen reduction will occur on the surface of both the copper and the iron. Environmental variations that may be important include oxygen concentration. since they lead to more damage to structures for a given loss of metal. However only the iron will be able to corrode.Localized Corrosion Learning outcomes – at the end of the course you should be able to … • Identify the main forms of localised corrosion • Provide simple explanations of the mechanisms of localised corrosion processes • Name chloride ions as a main environmental initiator of localised corrosion The various forms of localized corrosion tend to be a more severe problem than normal general corrosion. but the protection is incomplete. which results in corrosion fatigue.Page 1 . Mechanical factors that may be important include both static stress. Types of Localized Corrosion Galvanic Corrosion A extreme form of segregation occurs when two dissimilar metals are coupled together.2003. but only at the points of local breakdown. with consequent rapid attack. which leads to stress corrosion cracking. this may result in the same metal loss as in general corrosion. or by the effects of the mechanical loading experienced by the component. Corrosion and Protection Centre. Important metallurgical variations generally involve segregation of the alloying elements in the metal. pH and flow rate. chloride ion concentration. For example. Consequently if the areas of the two metals are the same. the iron will corrode twice as fast as it would in the absence of the connection to the copper. UMIST Module 0. Localized corrosion problems tend to occur most commonly when general corrosion has been limited by various means. Sources of Localized Corrosion Localized corrosion may be caused by variations in the environment seen by different regions of the metal. if a piece of iron is connected to a piece of copper in aerated sodium chloride solution. © 2002 . inclusions and grain boundary segregation.

18 Mo) Hastelloy C (62 Ni.662 Copper 2+ Mg-Mg -2.498 Platinum 2+ Pt-Pt +1.440 Monel (70 Ni. and this leads to intense local corrosion around the precipitates.277 Nickel (passive) 2+ Cd-Cd -0. 40-10 Ni) 2+ Zn-Zn -0. The EMF Series has the advantage of being based on a precisely quantifiable parameter.987 ? Graphite + Ag-Ag +0. 13% Cr (active) Cast iron Steel or iron 2024 aluminium (4.925 Hastelloy B (60 Ni.763 Bronzes (Cu-Sn) Al-Al3+ -1. The EMF Series (Table 1) and the Galvanic Series (Table 2) are often used to determine which metal of a couple is liable to corrode.2 Gold Pd-Pd2+ +0. 1.6 Mn) Cadmium Active or Commercially pure aluminium (1100) anodic Zinc ? Magnesium and magnesium alloys After de Bethune and Loud from INCO test results Similarly in an aluminium alloy containing iron. 32 Mo.126 Chromium stainless steel 11-30% Cr 2+ Sn-Sn -0. the iron-aluminium particles are good sites for hydrogen evolution. 15 Mo) H2-H+ 0. 30 Cu) 3+ Cr-Cr -0. Corrosion and Protection Centre.136 (passive) Ni-Ni2+ -0.337 Chlorimet 3 (62 Ni. Module 0. which is protected from corrosion by an insulating layer of aluminium oxide. 1 Fe) K-K+ -2. The Galvanic Series has been derived from exposure of samples in the specified environment. UMIST . 18 Cr. even the Galvanic Series should be used with some caution. 0. 7 Fe) 2+ Co-Co -0. Table 1 Standard emf series Table 2 Galvanic Series in Seawater o o Reaction E at 25 C.744 Cupronickels (60-90 Cu. However. consequently it gives a rather poor indication of the behaviour to be expected. (V vs NHE) Au-Au3+ +1.403 Silver solder Fe-Fe2+ -0.Page 2 © 2002 . 1 Mn) Inconel (active) Nickel (active) Lead-tin solders 18-8 Mo stainless steel (active) Ni-Resist (high Ni cast iron) Chromium stainless steel.5 Cu. 30 Mo.2003.000 18-8 Mo stainless steel (passive) 18-8 stainless steel (passive) 2+ Pb-Pb -0. Localized Corrosion . 17 Cr.714 Chlorimet 2 (66 Ni.788 cathodic Silver Cu-Cu2+ +0.799 Noble or Titanium 2+ Hg-Hg2 +0. 13 Cr. iron-aluminium inter-metallic particles will be precipitated in the aluminium. Unlike the normal aluminium surface.5 Mg.363 Brasses (Cu-Zn) Na-Na+ -2. as the severity of any galvanic corrosion since this depends on such factors as the electrical resistance of any passive films. 6 Fe. and therefore gives a better indication of practical performance.250 Inconel (passive) (80 Ni. but unfortunately passive metals may operate as stable cathodes at potentials well above the equilibrium potential. the conductivity of the electrolyte and the kinetics of the cathodic reaction on the cathodic half of the couple.

the solution both inside and outside the crevice will be oxygenated.Page 3 . Localized Corrosion . until eventually the passive oxide film can no longer be maintained. while the metal dissolution occurs over the entire surface of the sample. In this case the cathodic reaction of oxygen reduction only occurs at the site at which oxygen is readily available. Thus the solution in the crevice becomes more and more acid. when the structure is first immersed in seawater. for example. Considering. such as stainless steel. such as iron and copper. Crevice Corrosion and Deposit Attack For metals that are normally protected by a passive oxide film. leading to the production of positively-charged metal ions inside the crevice. sand etc. and severe corrosion occurs inside the crevice.2003.Differential Aeration Differential aeration occurs when two areas of a piece of metal are exposed to regions of solution of different oxygen content. and the corrosion rate of the steel will be low due to the protective action of the passive oxide film. UMIST Module 0. These react with hydroxyl ions to precipitate iron hydroxide. This further reinforces the acidification of the crevice. Correspondingly the metal dissolution reaction is accelerated in the oxygen-free region of the solution. Similar problems may also occur under deposits of dirt. the oxygen inside the crevice will eventually be used up by the slow corrosion occurring. the formation of forms of differential aeration cell by the presence of crevices in the structure can lead to very severe corrosion. with the result that the rate of metal dissolution at this site is retarded. The steel inside the crevice will continue to corrode. and the steel starts to dissolve actively. © 2002 . the use of stainless steel in seawater. However. the pH in the crevice goes down.. and in this case the resulting corrosion is called deposit attack. At the site of the oxygen reduction excess hydroxyl ions are produced. For many metals. Because of the removal of hydroxyl ions from solution by this process. this results in the deposition of a passive film of metal oxide or hydroxide. Corrosion and Protection Centre. causing the pH to rise. while the steel outside the crevice will continue to be in contact with aerated solution.

leaving a spongy mass of copper behind. For metals that are actively corroding. and may be quite dangerous.It should be emphasized that crevice corrosion requires a passive external surface in order to proceed. and the process as pitting corrosion. and retains the shape of the original casting.Page 4 © 2002 . such as carbon steels in seawater. Corrosion and Protection Centre. and in this case the crevice is protected from corrosion.nasa. which may have very different corrosion properties. but it is widely used). Localized Corrosion . which is relatively easily corroded. The resultant hole is known as a pit. the conditions in a crevice do not become acidic. which is essentially inert. which leaves a deposit of very finely divided carbon when it dissolves. Module 0. Pitting Under suitable circumstances a corrosion mechanism similar to crevice corrosion can occur on plain metal surfaces. the graphite is left behind. For various reasons the passive film breaks down locally. the region of solution in contact with the metal becomes acidic and starts to corrode rapidly. but the strength is markedly reduced. Dealloying Dezincification of brass – note the porous copper ‘plug’ and the continuous layer of copper (from corrosion.ksc. For example cast iron consists of iron. not conventional crevice Alloys are inherently made of dissimilar metals. UMIST . but these are due to the retention of moisture in the crevice. although the graphite has little strength. since the component appears to be intact. However in grey cast iron the carbon is present as flakes of graphite. and carbon. When this corrodes. Pitting corrosion of an aluminium tube. A similar process can occur with alloys such brass. from which the zinc can dissolve. because the accumulation of metal ions stifles further corrosion.2003. In normal carbon steels the carbon is dispersed in the steel as fine precipitates of iron carbide. Problems are experienced in crevices in carbon steel structures exposed in the atmosphere. This process is known as graphitic corrosion or graphitisation (some workers argue that the latter term relates to another form of degradation and should not be used here. Again this does not change the shape of the object.

Consequently grain boundaries tend to have different properties from the bulk of grain. and is a serious problem in welded structures. the structure can separate into a series of layers. Flow Effects Flow of solution tends to accelerate corrosion processes by increasing the rate at which oxygen gets to the surface of the metal (an exception to this occurs for passive metals. this precipitation tends to consume most of the chromium in the neighbourhood of the grain boundary. or immediately next to it (if the grain boundary is more noble). Corrosion and Protection Centre. and also diffusion of atoms is faster. Because of the irregular structure of the grain boundary it is easier to fit impurity atoms in. During rolling the grains in a metal tend to be flattened into a pancake shape. Exfoliation of an aluminium girder from a crashed WW 2 aircraft Stainless steels are corrosion resistant because of the chromium content. because of the much faster diffusion of carbon than chromium. Furthermore. It can be controlled either by reducing the carbon content to a very low level. Unfortunately however. When flow conditions become turbulent. for the chromium and carbon to combine to form precipitates of chromium carbide. the corrosion problems can become much more severe. This is known as exfoliation. which permits the formation of a thin. and the effective grain boundary chromium concentration is insufficient to keep the metal protected. Localized Corrosion . and often occurs with aluminium alloys. when the improved oxygen supply can help to maintain passivity). Erosion corrosion of a pump impeller © 2002 . and serious localized corrosion is often observed at joints and bends in pipework carrying water.Page 5 . if the steel also contains carbon. which form carbides in preference to the chromium. it is possible. Because of the faster diffusion in the grain boundary the precipitates form preferentially here. the chromium content must be greater than about 9%.Intergranular Corrosion Grain boundaries in metals and alloys tend to be sites of significant changes in composition. This leads to enhanced corrosion either at the grain boundary (if it is less corrosion resistant than the grain).2003. In order for the steel to be corrosion resistant. and if such an alloy is subject to intergranular corrosion. highly protective film of chromium oxide on the steel surface. or by adding elements such as titanium or niobium. The resulting corrosion is known as intergranular corrosion. For this reason stainless steels have chromium contents that are typically in the range 13 to 20 %. if the steel is heated to a certain temperature range. UMIST Module 0.

both of which further enhance the transport of oxygen to the metal surface. and also tend to mechanically damage and remove protective films of corrosion product. the action of mechanical stress can enhance corrosion and related processes.2003. but as soon as plastic deformation occurs. If the solution velocity becomes high enough. Localized Corrosion .More serious problems can occur if the fluid contains entrained air bubbles or particles of solids. Corrosion and Protection Centre. In the case of a static stress the resultant failure is termed stress corrosion cracking. These processes are known as impingement and erosion-corrosion. One aspect of this aspect of this interaction is the enhanced failure of metals by cracking in the presence of stress. Additionally. UMIST .Page 6 © 2002 . Mechanical Aspects of Corrosion It is often found that the joint action of corrosion and mechanical stress is more damaging than either alone. vapour bubbles may form at low-pressure regions. while rubbing surfaces may suffer from accelerated corrosion known as fretting corrosion. Thus mechanically deformed metal tends to corrode more rapidly. either because the oxide film which normally limits the rate of corrosion is disrupted by the deformation. while for alternating stresses the process is called corrosion fatigue. The subsequent collapse of these leads to a combination of corrosion and mechanical damage known as cavitation. Stress Corrosion Cracking Stress corrosion cracking of a large stainless steel float Module 0. The Effect of Stress and Strain on Corrosion Elastic stress does not usually cause much change in corrosion behaviour. the metal tends to become significantly more active. or because the greater number of dislocations in the strained metal make the corrosion process easier.

such as: • Welding. carbonate/bicarbonate. especially in the presence of sulphides. Because of the need for a fairly delicate balance between the tendency to corrosion and the generation of plastic strain. Liquid Metal Embrittlement A process similar to stress corrosion cracking can occur if liquid metals come into contact with a metal. For example mercury will cause brass to crack. The reasons for this are not known. and stainless steel will crack in liquid zinc. Localized Corrosion . are less susceptible to hydrogen embrittlement. The mechanisms by which this is thought to happen are similar to those of stress corrosion cracking and hydrogen embrittlement. Common systems giving rise to stress corrosion cracking are: • Brass and ammonia (often in local atmospheres). In general higher strength materials are more susceptible to hydrogen embrittlement. and the plastic strain causing the corrosion. When combined with a corrosive environment the process is known as corrosion fatigue. the major problems occurring with high strength steels. but because of the more extreme mechanical damage. with the corrosion causing the plastic strain.If the rate of corrosion at sites at which the protective oxide film is ruptured is sufficient to cause more plastic strain at the tip of a notch or crack. although it seems probable that the stress corrosion cracking of high strength aluminium alloys in water is a hydrogen embrittlement process. Corrosion Fatigue The process of metal fatigue is responsible for the majority of mechanical failures. the environments in which the effects are seen are far less specific. © 2002 . • High strength aluminium alloys in water or water vapour. As a general rule face centred cubic materials. but this leads to many problems that are similar in result to stress corrosion cracking (indeed the latter term is often used to cover both types of failure). nitrate and phosphate solutions. so we find more cases of problems. but one that reforms slowly when damaged. This process is called stress corrosion cracking. but in general the effect is to increase the rate of both processes. • Austenitic stainless steels and chloride solutions (70°C). UMIST Module 0. • Carbon steels in caustic. • Corrosion. this phenomenon is observed only in specific combinations of metal and environment. A general requirement is that the metal should be protected by a good passive film. it is possible for this enhanced corrosion to propagate into the metal. Hydrogen Embrittlement Many metals are made brittle by the presence of dissolved hydrogen. The hydrogen may come from many sources.Page 7 . although as our knowledge of the subject increases. The effects of corrosion on fatigue crack initiation and growth are still not fully understood. such as austenitic stainless steels. • Electroplating.2003. Corrosion and Protection Centre. • Contact with gaseous hydrogen.

Page 8 © 2002 .2003. and which reduces the rate of corrosion. This process. Corrosion and Protection Centre. the oxide film which is normally present. is known as fretting corrosion.Fretting Corrosion If two metal surfaces are rubbed together. Localized Corrosion . may be removed. particularly if the amount of movement is small. UMIST . which can lead to very rapid wear of mating surfaces. The oxide debris may also act as an abrasive. and the oxide remains in the joint. Module 0. thereby allowing corrosion to occur more quickly.

2003.Page 9 . Corrosion and Protection Centre.© 2002 . UMIST Module 0. Localized Corrosion .