1 Corrosion Objective When you have gone through this chapter, you should be able to + explain how corrosion affects metallic materials explain which factors influence the corrosion process use the galvanic.series to determine the risk of galvanic corrosion when metals are joined together distinguish between different types of corrosion and describe their characteris- tic features. Introduction Annually corrosion costs society vast sums. In the Western World the costs have been estimated to constitute approximately 3-4% of the gross national product. ‘A major part of the damage is due to too little knowledge about corrosion and the conditions which cause corrosion. If the selection of materials is not considered carefully enough, the result can be extensive corrosion damage. It has been esti- mated that improved knowledge about corrosion and corrosion protection can re- duce costs by approximately 15%. In case of corrosion protection by means of paint coatings the applicator and the inspector are important. In order to ensure that the job is carried out correctly they must have a good understanding of subjects like corrosion, surface preparation and protection against corrosion. Later in the book these subjects will be discussed in greater detail. What is corrosion? It is a common opinion that corrosion is the same as rust, which is not entirely true. Rust is the corrosion product formed when iron and steel corrode. But many other materials are also attacked. The patina on copper and white rust on zinc are well- known examples. These are also corrosion products. Consequently, corrosion is the deterioration or breakdown of materials due to a reaction with the environ- ment. Besides destroying metals, corrosion also contributes towards breaking down concrete and plastic materials. Why, then, are a number of construction materials around us broken down, and how does this happen? If we look at the metals, most of them are produced by 1 Corrosion 15Sheets Pipes Energy Water Manufacture Onygen aw materia (oo ENE) Fst Figure 1.1 Production and deterioration by corrosion of iron/stcel In the manufacturing of metals energy is applied to the raw material, ore. During the process the ore melts and the metal is separated from the slag products. Milling takes place while the metal is in a red-hot state. During milling the red-hot stee! gets into contact with air and a thin layer is formed on the surface. This layer is usually called mill scale. Mill scale is brittle and only protects the metal as long as it is intact. If the steel is left outdoors, the mill scale will eventually crack and the steel begin to rust. By this breakdown, the corrosion, steel is transformed into rust. Chemically speaking, rust has almost the same composition as ore. The process has now come toa close. It started with ore and has now ended up with rust. The iron is again at a lower and more “natural and stable” state of energy. Metal production can be compared to a ball placed at the foot of a hill. By applying energy we move the ball uphill. When the ball is placed on the ground at the higher level, it will start rolling until ii reaches the lowest level and stops. Innature oo cra 3 Ore Oo Stable condition Figure 1.2 This is what happens: The ball, which was at a stable level, was transferred to a non-stable level. Due to physical reasons the ball rolls down the hill and finally comes to a halt at the foot of the hill. The ball will again be at its most stable level. 16 Corrosion proTEcTIONIn principle, this is also what happens during the production of metal. To extract the metal, found only in limited quantities in the ore, energy is required. Due to the energy expended, the metal in the ore is transferred from its stable level to a non- stable level. The metal has now been extracted from the ore, but external conditions like moisture and oxygen cause the corrosion process to start. The corrosion proc- ess is a natural process which under the right circumstances (i.e. oxygen supply and high humidity) tries to convert the metal back to its most stable state, which is ore. The chemical compositions of ore and the corrosion product are very much alike. If we want to preserve the metal, something must be done. In order to prevent the corrosion process from starting, we use paints, coatings and linings, or other barriers to stop any direct contact between the metal and the environment. Oxygen Water oe a Mit scate — Steel Figure 1.3 Eventually mill scale will crack and the steel begin to corrode Corrosion theory In order for a mietal 10 corrode the surface of the metal must be covered by an electrically conductive liquid or substance (electrolyte) and oxygen. Water, either fresh water or sea water, and soi] are examples of electrolytes. Pollution in the air may dissolve in water and make it conductive. Metals have a tendency to release electrically charged atoms (ions) when in contact with water. For some metals this tendency is weak, for example in the case of platinum and gold. Such metals are called noble metals. Other metals release a large number of ions in contact with water, for example aluminium and zinc. Such metals are called ignoble or base metals. If we immerse two different metals in a conductive liquid (an electrolyte) with- out any electrical connection between them, both metals corrode at a certain rate. But if the metals are joined together electrically, the rate of corrosion increases on the less noble metal. How fast the corrosion takes place depends on a number of factors, including the metal types, for how long humidity is present, pollution on the surface, etc. Table 1.1 gives the corrosion rate in pm/year (thousandth millimetre per year) for the metals steel, aluminium, copper and zinc after two, five and ten years’ exposure at a testing station on the west coast of Sweden. The corrosion of the metals takes place at very different rates, which is mainly due to the formation of oxide films and corrosion products on the metal surfaces. It can also be noted that a porous corrosion product like rust to some extent results in a reduced corrosion rate over time (given in ym/year). QWZyears op years lu years _ Steel 62 328 ~~ 207 Aluminium 0.48 0.76 0.35 1.8 0.71 3.6 1.7 In order to explain this in more detail. think of an example where iron is in contact with copper in an electrolyte. When an iron atom leaves the metal surface. it re- leases two electrons and becomes an iron ion. The sites where this takes place are called anodes, The anode is consumed by corrosion. The electrons pass through the iron to the copper - the cathode. At the cathode hydroxyl ions are formed, which combine with the iron ions. Afier this. a reaction takes place with oxygen in the air to produce rust, which may be called water-containing iron oxide. Voltmeter 4 pees Copper, emt lon (cathode) — {anode) Rust Figure 1.4 Corrosion of the less noble of two metals increases if the metals are connected in an electrolyte Zine case Carbon rod ‘Ammonium chloride and zine chloride Paper ‘Manganese oxide and pulverized carbon Figure 1.5 A dry cell battery illustrates the corrosion process 48 — Corrosion protectionA simple illustration of the corrosion process is provided by the activity within a dry cell battery. The dry cell battery consists of a carbon or graphite rod in substance able to conduct electricity (an electrolyte). This substance is enclosed by azine case. The carbon or graphite rod is more noble than the zinc case. If a small light bulb is inserted between the poles of the battery. it will light up. The battery supplies the power. When in use. the battery is being discharged. This is because the zinc case (the anode) corrodes. If the process is allowed to continue Jong enough. the battery will eventually stop working and could start to leak. The corrosion process has corroded the zinc cuse surrounding the electrolyte. Conse- quently. the less noble of the two metals in contact has broken down and. being the anode. Zine has delivered the energy to the cathode: However. in order for corrosion to take place. it is not necessary that dissimilar metals are joined, ay in this example. It is a well-known fact that steel rusts if exposed outdoors in wind und weather. The reason is that steel is not microscopi- cally uniform. I contains a number of small areas with noble and base particles. On unpainted steel mill scale. graphite grains. or other noble particles tend to be- come small cathodes. while the bulk material (the steel) becomes the anode. These areas form among themselves small corroding “batteries”. The corrosion attacks enoble areas on the steel (anodes). At the cathode there is no breakdown of the metal. but the solution around the cathode becomes alkaline + (Cathodes) > (Anoges) Figure 1.6 A steel surface consists of numerous areas with noble and base parti- cles. Among themselves these areas form small “batteries” In simple terms. the corrosion process can be described as follow: iron + oxygen + water — iron ions + hydroxyl ions —> iron hydroxide (rust) The iron ions and the hydroxy! ions react with one another and form rust. ‘At the cathode there may also be other reactions than the formation of hydroxyl ions. In acidic solutions (acids) hydrogen gas is formed. Deposit of noble particles from a solution at the surface of the metal may also be a cathode reaction. Tt is important to note that if we can prevent the metal surface from getting into contact with air (oxygen) and an electrolyte (water), we are actually able to prevent corrosion. This is to a great extent utilized in practice. Just think of closed water-filled systems where there is little exchange of the water, for example in central heating systems (radiators) in blocks of houses and office buildings. The limited quantity of S:oxygen present in the water when the system is taken into use is quickly consumed due to corrosion. When the oxygen has been consumed, the corrosion attack within the system ceases. There are many ways in which we can prevent metal surfaces from getting into contact with moisture. For example. surfaces can be painted or applied with other types of coatings. But it is also practically possible to remove or reduce humidity in closed-in constructions to such an extent that the formation of a conductive water film is not possible. This principle is used world-wide on bridges made as steel box girder constructions. Outside, the steel construction can be applied with a duplex system in the form of thermally sprayed zine coating and paint, but inside the steel is only primed. A dehumidifying system ensures that the relative humidity inside the structure is constantly approximately 40%. The idea is that at such low relative humidity the formation of an electrolyte inside is not possible. This prevents any internal corrosion. Electrochemical series The corrosion resistance of a metal indicates the ability of the metal to resist cor- rosion in a defined environment. How resistant metals or alloys are,'depends on factors such as the type of metal and the environment to which it is exposed. Inall metals or alloys (mixtures of metals) a certain amount of energy is stored. This amount of energy can be measured in volt. These measurements are usually called potential or voltage measurements. The difference in potential between two metals can be measured by a voltmeter. Howevei, in order to measure the potential of the metals, either alone or together, a reference electrode must be used. A reference electrode serves as a kind of zero point. Such a reference electrode is called the standard hydrogen electrode, often abbreviated SHE. It has a potential of 0 V in a defined solution at 25°C. Steel- Reference electrode Figure 1.7 Potential measurement with reference electrode For potential measurements in sea water the reference electrodes listed below are used. When a certain reference electrode is referred to, the chemical names or the abbreviations in the parentheses are occasionally used. 20 — Corrosion PROTECTIONTable 1.2 Potentials for different reference electrodes in relation to the standard hydrogen electrode (SHE) [ Reference electrode Electrolyte Potential versus SHE (V)_| | Zine Sea water —_ approximately -0.78 V | Silver/silver chloride (SSC) Sea water approximately +0.25 V Copper/copper sulphate (CSE) Sea water approximately +0.32V | Calomel (SCE) Kc! approximately +0.245 V_| Tucan be seen that a reference electrode of zinc is negative compared to the standard hydrogen electrode, and that the other three are more positive. Metals and alloys can be ranked in electrochemical series according to their corrosion resistance. Such electrochemical series are established by measuring the potential of a metal or an alloy in a defined environment. The most widely known and used series is the galvanic series in sea water. A closer Jook at the galvanic series quickly reveals which of two joined metals will corrode. Table 1.3 shows that both zinc and aluminium and their alloys are less noble than steel. If two metals are placed in electrochemical contact, the less noble metal will suffer increased corrosion. This circumstance is of great practical importance. for example in connection with corrosion protection. For this reason, alloys of zinc, aluminium and magnesium, which are all less noble than steel, are used for ca- thodic protection of steel structures. The lowest possible rate of corrosion is desired when two metals are joined. In order to achieve this, the metals must be insulated from each other in such a way that they are not in direct electrical contact. If this is not possible, it must be en- sured that their relative positions are not too far apart in the electrochemical series. The driving force behind corrosion processes has been mentioned, i.e. the differ- ences in potential between the metals. The greater the difference in potential, the fiercer the attack will be on the less noble of the two metals. To a very large extent the corrosion attack on a metal also depends on the me- dium or environment to which it is exposed. Aluminium alloys and stainless steel alloys do not corrode to any great extent when exposed in urban or industrial at- mospheres. However, the attack may be important if the same alloys are exposed to. for example sea water. In the galvanic series a few metals or alloys are listed twice. This is due to the fact that some metals are covered by a thin and protective oxide film. As long as this oxide film is intact, it helps the metal to remain passive. If the film has been removed or damaged, for example through abrasion, the position in the galvanic series changes. The metal now has a higher tendency to corrode. Metals with such an oxide film include stainless steel, nickel alloys and alu- minium alloys. If there is plentiful supply of water and oxygen, these oxide films are self-repairing. Under layers of dirt and pollutants the supply of oxygen may become too low. In such sites the oxide film is not repaired and corrosion may occur. Under such conditions, some process industries have experienced problems with crevice and pitting corrosion of “ordinary” stainless steel. This has resulted in a change to higher grade stainless steel types, for example ASTM $31254. 1 Corrosion 21Table 1.3 Galvanic series in flowing sea water (2.5-4 m/s), temperature range 1]- 30°C. Potentials are measured versus saturated calomel reference electrode (SCE) [2] +03 +01 FG GF -06 ry +02 Eaten Grn jonah (G4 M1 20-10 Coope fea To.a0 Copper Nickel Nxet-Aiominar Bronse Miekel-Cnromum fer Bae Mile ie Bice Staiie ac hi-Copre ays S050 Crevice and pitting corrosion are types of corrosion which cause localized corro- j sion attacks on metals. The attack often starts where there is a poor exchange of electrolyte in narrow crevices or in pits. This type of attack often takes place very : quickly and may result in the metal corroding completely through. Galvanic corrosion is also found if the external conditions between two equally noble metals result in a difference in potential. Such a difference may occur due to a difference in oxygen concentration. for example on piles submerged in sea water. 22 Corrosion PROTECTIONGalvanic corrosion is a type of corrosion which occurs when there is metallic con tact between two metals in a corrosive environment. The selection of appropriate materials requires thorough knowledge of metals and alloys and their behaviour in different environments. Corrosion environment and pH Indoors, in dry rooms, there is little danger of corrosion because there is no con- tinuous electrolyte being formed on the surface. In the case of outdoor exposure. the corrosion attack depends on the environment. The more polluted the environ- ment, the faster the corrosion attack will be. Many of the industrial gases emitted into the atmosphere are transformed into acids or alkalis. Such solutions attack metals as well as other construction materials. In order to indicate whether a solution is acidic or alkaline, the pH value of the solution is measured. The pH value is usually measured within a range from 0 to 14, Pure water has the pH value of 7, which is a neutral solution. If a pH value of Jess than 7 is measured, it is an acidic solution. The closer to 0, the more acidic the solution. Rain water often has a pH value around 5 because it has taken up acidic pollution. ‘ The pH scale is logarithmic. This means that for every single point above or below a pH value of 7, the solution will be ten times more concentrated. A solution with a pH value of 5 is consequently 10 x 10 = 100 times more concentrated than a neutral solution with pH value 7. Acidic | = aikaline Neutral eet 10 11 12 13° 14 Figure 1.8 The pH scale Alkaline substances have pH values from 7 to 14. Examples of such substances are sodium hydroxide (caustic soda, lye), ammonia and cement. Acidic substances have pH values from 0 to 7. Examples of such substances are hydrochloric acid and sulphuric acid. Their area of use includes pretreatment (pick- ling) of steel before hot dip galvanizing. The corrosion attack on metals is often intensified in acidic and alkaline solu- tions. Both aluminium and zinc sustain very severe attacks in contact with alkalis. However, if steel is immersed in an alkaline solution, the steel is passivated. A thin iron oxide film is formed on the surface which offers good protection against corro- sion, and the rate of corrosion is reduced considerably. Reinforcing steel bars are well protected and kept passivated by the alkaline environment in concrete. The decisive factor for the corrosion process is whether water from rain, dew or condensation due to a high relative humidity of the air is present on the metal surface. However, the consequences may vary considerably. When it rains, contaminants like salts and dirt collected on the surface will be 1 Corrosion 23washed away. But in case of high humidity or condensation on the steel, such con- taminants are not washed off. Contaminants in the form of dust and salt attract moisture (they are hygroscopic), and this prolongs the time of wetness. For this reason, structures in an environment of high humidity, but little precipi- tation, may sustain severe corrosion attacks. Aluminium Zine Stee! Iron oxide Alkaline solution Figure 1.9 Contact with strong alkalis will cause attack on both zinc and alu- minium, but not on steel Corrosion types So far the deterioration of materials by the process of corrosion has been described in very general terms. In the case of corrosion on metals, the attacks are usually given a more detailed characterization, primarily based on the appearance charac- teristics of the attack. A more detailed description will now be given of some of the most common types of corrosion found on metals. Uniform corrosion (general corrosion) When corrosion develops at approximately the same rate over the entire metal sur- face, it is called uniform corrosion. This type of corrosion results in a fairly even breakdown of the metal. An attack like this causes both anode and cathode reactions to occur on the same metal. Areas of different nobleness can be found due to particles of foreign metals being present in the metal surface or in the electrolyte. Technically speaking, this type of corrosion is not very problematic. The life- time of various alloys in various environments can be calculated. If the attack takes place at a rate of approximately 0.1 mmv/year, it will take 20 years before a metal thickness of 2 mm has corroded away completely. Normally Fequirements to both strength and lifetime are taken into consideration and the metal thickness increased by a corrosion allowance. Figure 1.10 Uniform corrosion 24 — Corrosion pRoTECTIONAn old galvanized roof where the zinc has corroded away is an example of uniform corrosion, Attacks on low alloy and weathering steels are often of this type. This corrosion type can be seen on most metallic materials. Uniform corrosion can be reduced by selecting the right material adding inhibitor (to systems carrying liquid) using cathodic protection using coatings/linings Galvanic corrosion (bimetallic corrosion) One of the most widely observed corrosion types, and often the most dangerous type, is galvanic corrosion. This type of corrosion occurs when there is metallic contact between two metals in a corrosive environment. The corrosion is acceler- ated on the base metal and is reduced on the noble metal. Cathode ‘Anode Figure 1.1] Galvanic corrosion The attack on the base metal, the anode, is most severe close to the point of contact and decreases with increased distance from it. The driving force behind galvanic corrosion is the difference in potential be- tween the two metals. The attack is severe if metals located far apart in the electrochemical series are joined together. The appearance characteristics of the attack depend on several factors. The relative area sizes of the anode and cathode and the conductivity of the electrolyte are among the most important factors. A large cathode coupled to a small anode often leads to a faster and more severe corrosion attack than in the case of a small difference in area. The offshore oil industry has experienced problems with some types of welding electrodes used for welding of carbon steel. By accident insufficiently alloyed elec- trodes compared to the pipes were used. This resulted in complete corrosion of the welded joints in record time and extensive damage to the materials. The reason is galvanic corrosion caused by a large cathode area (the pipes) and a small anode area (the welds). The galvanic series in sea water (see Table 1.3) was mentioned above. To a certain extent this series provides a possibility for predicting the risk of galvanic corrosion. Below some examples of various types of attack caused by galvanic contact between dissimilar metals will be discussed. The Statue of Liberty in New York City was completed in 1886. The copper statue was supported internally by a framework of iron and steel. The copper skin and the steel were originally insulated from each other by means of asbestos fabric impregnated with shellac. Over the years the asbestos fabric had deteriorated and started to work as a wick between the metals. In the early 80's the steel framework 1 Corrosion 25had become extensively damaged due to galvanic corrosion. The corrosion attack on the steel and cracking of the rust had caused deformation of the copper skin ina number of places. ; During the restoration an effort was made to prevent galvanic corrosion. Most of the steel was replaced by stainless steel alloys and the metals were insulated from each other by means of Teflon gaskets/inserts. [3] A number of wheel houses on ships are made of aluminium. This has resulted in galvanic corrosion in the interface between steel and aluminium, but the prob- lems have now been reduced by changing the joining techniques and by using anticorrosion paints. Galvanic corrosion can be reduced by using filler metals for welding which are nobler than the parent material changing the materials used in order to avoid harmful contacts between noble and base materials insulating materials from each other using metal coatings or paint coatings avoiding the deposit of nobler metal ions on the surface. Crevice corrosion Narrow crevices exposed to a liquid, typically water-containing solutions, may be open enough to allow the liquid to penetrate, but still so narrow that the liquid becomes stagnant within them. If this is the case, crevice corrosion may occur. The driving force for this type of corrosion is a difference in oxygen content inside and outside the crevice. ‘The most pronounced crevice corrosion occurs on metals which are passive or easily passivated, such as stainless steel, aluminium and steel in predominantly alkaline envirofinents. For example in sea water the passive oxide layer on some metals may be broken down by aggressive chloride ions. Crevice corrosion occurs in flanged joints, under rivet heads and screw heads, in overlaps and when the metal is covered by for example dirt, sand, corrosion products or marine growth. Water more rich in ‘oxygen becomes the cathodic region ‘The crevice becomes the oxygen depleted area, i.e. the anodic region Cathodic reaction: 440, +H,042e=20H- Figure 1.12 Crevice corrosion 26 — CoRROSION PROTECTIONIn some cases crevice corrosion in flanged joints or beneath rubber hoses mounted by clamps onto stainless steel piping in sea water has had an extent of several millimetres per year. The reason is that sea water has penetrated but the exchange has not been frequent enough, which again leads to too low oxygen content to maintain the oxide film. Crevice corrosion DZD DPTDELIE: Figure 1.13 Crevice corrosion on stainless steel Crevice corrosion can be reduced by a number of practical precautions: - Use welding instead of flanged joints and bolted joints whenever possible. - Minimize the number of sharp edges, corners and possibilities for liquid pock- ets. Drain areas which are not continuously filled with liquid. Do not use packings that absorb water. Take solid particles and suspensions which may adhere to the walls into consid- eration. Pitting corrosion Pitting corrosion is a type of corrosion which involves localized attacks on metals. The attack is in the form of localized pits. This corrosion type may arise on a number of metals, but it is often found on metals with a passivating oxide film, like aluminium and stainless steel. Such attacks may result in extensive damage. Often Zz__|OoO Figure 1.14 Piting corrosion The relative sizes of the cathode and anode areas also determine the corrosion rate. The larger the cathode area relative to the anode area, the more severe the attack. The problem is also related to defects either in the oxide film or otherwise in the material. Attacks on stainless steel are often more severe than on ordinary steel. If the oxide film is attacked by chloride ions, it will be on weak spots in the film. The difference in area between the cathode and the anode is consequently very big. Ordinary stee] has considerably more defects and the cathode and anode areas will be more equal in size. The oxide film on the stainless steel has few defects and acts as cathode to the metal. The corrosion rate inside each pitting can be considerable and may cause the material to corrode through relatively quickly. Pitting corrosion is often seen in conditions where the metal is passive. Pitting corrosion may also act like bimetallic corrosion. This happens when the water contains traces of more noble metal ions which are deposited on the metal surface. Major corrosion attacks may take place when copper ions are deposited as metallic coppet on aluminium and steel. Also a fairly noble material like copper may experience pitting corrosion. In copper pipes this may be due to the water quality or deposits from the water. Also residues in the pipes of carbon-containing drawing agent from the manufacturing process may be the reason. Heating of the pipes during their fabrication causes it to carbonize and a thin layer of carbon or graphite may be left on the walls of the pipe. Graphite is more noble than copper. The difference in area size between cathode and anode is big, and often major corrosion attacks are seen. Some materials are highly resistant to pitting corrosion. They are usually char- acterized by a high content of chromium, nickel and molybdenum. Other metals are susceptible to this type of corrosion in chloride-containing environments and are, for example, not used in sea water nor in the chemical process industry. In chloride-containing environments ordinary stainless steel usually has too lit- le resistance against corrosion. On the other hand, special high alloy, stainless and acid-resistant steels, copper-nickel alloys and nickel and titanium alloys can be used with excellent results. Pitting corrosion can be reduced or prevented by selecting more suitable materials changing the corrosion environment 28 — Corrosion PROTECTIONAnode Cathode Anode Electrolyte with high conductivity ‘Anode Cathode ‘Anode Electrolyte with low conductivity Cathode Anode Cathode Figure 1.15 The corrosion attack is determined by the relative area sizes of the cathode and the anode, and by the conductivity of the electrolyte Erosion corrosion Erosion corrosion is a type of corrosion which occurs when a metal is exposed to mechanical abrasion and a corrosive environment at the same time. Liquid or gas flowing at high velocity in pipes may cause erosion corrosion. Turbulence is formed in the pipes. The mechanical impact causes the protective surface layers to be worn off or damaged at the surface. Erosion corrosion may occur on most metals, but copper alloys are especially susceptible to this type of corrosion attack. Depending on the temperature of the fresh water, the maximum water velocity in non-replaceable distributing pipes is 1- = 2 m/s, perhaps slightly higher on coupling pipes, before erosion corrosion arises. Copper alloys are also widely used for transport of sea water. These velocities for sea water should not be exceeded: copper alloys I ms aluminium brass 1.8 m/s copper-nickel alloys _2.5-3.5 m/s Erosion corrosion is often due to the fact that the construction has an unsuitable design. Inside the pipe the corrosion can be caused by uneven weldings or pipes, inserted by welding, which jut in too far and thereby cause the flow of the water to change. Over time this results in a sort of undermining of the material. The attack is often shaped like a horse shoe.ie | , ec i Figure 1.16 Erosion corrosion on copper Selective corrosion (dealloying corrosion) Selective corrosion can appear on brass and cast iron if they are exposed in sea water. This type of corrosion causes one of the alloying elements to be preferen- tially attacked. The attack may be local or uniform over the entire surface. As a result, the geometry of the object may remain unchanged, but since one of the elements has been removed, it leaves a porous material with little or no mechanical strength. Well-known examples of selective corrosion are the dezincification of brass and the graphitization of cast iron. Brass is an alloy of zinc and copper. Certain brass alloys with a high content of zinc are susceptible to selective corrosion. If such an alloy is used in sea water, the zinc will corrode and leave a porous matrix of copper. Consequently, the brass has lost its strength. Once the attack has reached this stage, only small impact is re- quired to cause for example a pipe to break. When brass is dezincified, the attack can be seen as small reddish-brown areas on the brass. Here the zinc has corroded and the visible spots are the porous matrix of the copper. No corrosion LLLLLLLLLLL LLL LLL LL Selective corrosion (pitting corrosion) Selective corrosion (of the surface) LLLLLLLLLLLLLLLLLLLLLL Selective corrosion (of all the material) Figure 1.17 Selective corrosion 30 Corrosion PROTECTIONCast iron has a high content of carbon. Graphitization results in corrosion of the iron, leaving a porous matrix of carbon in the material. As a result of the attack the iron in the cast iron will disappear and leave a dark area consisting of graphite (carbon). This may happen if cast iron is immersed in sea water. Stress corrosion cracking Stress corrosion cracking (SCC) is a term given to inter- or transgranular cracking of metals by joint action of static tensile stress and a specific environment. This type of corrosion is very common in many industries. Great concern has been given to SCC both on onshore and offshore locations. Different types of metals or alloys will be more or less sensitive than others to a given solution or environment. Metal Solutions causing SCC Carbon steel Nitrate solutions (NO,’) Copper alloys Ammonia solutions (NH,) , Stainless steels Chloride solutions (Cl) © Insulated stainless steel pipes for the transport of fresh water or sea water at tem- peratures of approximately 60°C are particularly susceptible to stress corrosion cracking. Such pipes are often insulated with cellular glass insulation. Before ap- plying the insulation, the stainless steel is often sweep-blasted with a fine mineral abrasive and then painted with epoxy or similar coatings. It is common practice to specify paints without zinc metal or chlorine-containing constituents. The risk of stress corrosion cracking on stainless steel can be reduced by stress- relief annealing to remove residual stresses from welding or cold-work. Cracking Figure 1.18 Stress corrosion cracking on stainless steel in chloride-containing environment at 60°CAMO USLUPI HILAL BlaD, AU ZLatuI Wan Geeuds eCuS He oF — of the metal. This type of corrosion especially affects austenitic stainless steel with a carbon content of approximately 0.05-0.08%. for example of the ASTM 304 and ASTM 316 types. These types of steel may be susceptible to corrosion attacks if they have been subject to heat treatment within the temperature range of 400-800°C. The heating causes a deposit of chromium carbide on the grain boundaries. This deposit takes place at the expense of a small zone on the grain boundary where chromium contents are reduced. In this little zone the material loses its “stainless-ness”, so to speak. Intergranular corrosion of austenitic steel often takes place in connection with welding. The areas around the welds are often subjected to the relevant temperature range for a short period of time. This results in a localized attack around the weld. on both sides of it. Intergranular corrosion usually occurs in very specific environments, for exam- ple chloride-containing environments. In order to avoid this type af corrosion it is common practice to select a material quality like ASTM 304L or 316L with a low content of carbon (lower than 0.03% C). or other alloys stabilized with titanium or niobium which bind carbon and form titanium or niobium carbide instead of chro- mium carbide. UMMM«a Figure 1.19 Intergranular corrosion Corrosion fatigue ‘When a metal is subjected to either temporary or continuous stresses, cracking may suddenly occur above a certain stress level. This may take place in spite of the stresses being considerably smaller than what is otherwise known to be the tensile stress of the material. This is usually called fatigue. When this fatigue takes place in a corrosive environment, it is called corrosion fatigue. In the case of corrosion fatigue the material may be broken down earlier than in the case of ordinary fa- tigue. Corrosion fatigue causes cracking of the material and total destruction may be the result. Microscopes are often used for the evaluation of the surface of the frac- ture. In this case lines can be observed on the smooth part of the surface, so-called striations, The striations have the same curvature towards the starting point. 32. Corrosion PROTECTION<— Dynamic stress Figure 1.20 Fatigue corrosion Corrosion in different environments Corrosion in air Corrosion of unpainted steel or other metals takes place at a relative humidity higher than approximately 60-70%. Because the air contains oxygen, the decisive factor for the corrosion is how long the metal surface is wet. The length of time when the surface is wet is usually called the time of wetness. The time of wetness is defined as the period of time when the relative humidity of the air is above 80% and the air temperature above 0°C. In urban and.industrial atmospheres there is a particularly high amount of solid particles in the air, including soot, sand and chloride and sulphate salts. Such salts are hygroscopic {attract water) and water soluble. Thereby they increase the corro- sion in air. In some cases it is also a determining factor for the corrosion attack whether the water on the metal surface is due to condensation or rain. In very polluted environ- ments rain will wash away contaminants. Condensation rarely creates so much water that the contamination is actually washed off the surface. Corrosion attacks caused by condensation may be more severe than those caused by rain water. The corrosion rates of for example aluminium alloys, stainless steel, copper alloys and zinc are generally lower than of steel exposed to the air. Corrosion in water Structures to be immersed in water are often built of metallic materials. There are two main types of water: fresh water and sea water. Corrosion attack in water depends on the temperature, pH value and oxygen and salt contents of the water. Fresh water In areas of the world where the drinking water is soft, with a low calcium content, the water is corrosive. At a number of waterworks attempts have been made to reduce the internal corrosion of the water piping system. Such attempts include increasing the calcium contents and the pH value of the water. Hard water is less‘As opposed to this, pure sea water in the oceans of the world has a constant compo- sition and corrosivity. The salt content is approximately 3.5% and pH 8.1. [4] From the chloride contents of the sea water a relatively high corrosion rate for steel should be expected. But to some extent the contents of calcium and magnesium salts reduce the attacks. Such salt layers have a protective effect. This is especially the case in connection with cathodic protection where the formation of hydroxide results in increased pH value and deposit of calcium and magnesium salts on the surface. Corrosion is oxygen dependant and will be severe in the splash zone since the water is continuously enriched with oxygen. At the same time the salt deposits are washed away. and the effect from the deposited salt layer is reduced. Also the velocity of flow may be of importance for the attack on some alloys. A high flow velocity causes the protective layer of corrosion products to be worn away. In extreme cases also parts of the actual material may be torn away. Espe- cially copper alloys are susceptible to this type of corrosion, which is called ero- sion corrosion. On stainless steel the risk of such attacks is very small. At too low velocity of flow or in stagnant liquids crevice corrosion may occur. Corrosion in soil Structiires which are fully or partly buried in soil will be exposed to corrosion. The attacks in soil will to a very large extent depend on the type of soil and humidity, salt and oxygen contents, pH value. etc.. and may be quite extensive. In order to reduce the extent of the corrosion it is important that the soil around buried structures is well drained. This is the case of gravel, sand and moraine. In such types of soil the oxygen contents are consequently high. Ground level Ti oT -Cathode "=" Anode. corrosion Cathode! a Sey = Cable or pipe Soil, sand, gravel Clay Sand, gravel Oxygen contents: High Low High Electrode reaction: 0,+2H,0+4e-+40H Fe-aFe?+2e 0,+2H,0+4e+40H : Po4Pb*+2e etc. Figure 1.21 Corrosion attack in soil 34 — Corrosion protectionIn mixed clay-containing soils variations in the oxygen contents may occur. Clay Jumps near the surface result in low supply of oxygen. In such places there is a risk of localized corrosion attacks. Structures to be placed fully or partly in contact with soil over a prolonged period of time, should if necessary be protected. This especially applies to steel. which is often protected by thick organic coatings of coal tar or rubber. Alloys of lead and copper have better resistance to corrosion in soil. Literature 1 Torsten Johnsen and Cecilia Aronsson: Korrosionshastigheten hos fas Slutraport. Kl-report 1995:7. Korrosionsinstitutet, Stockholm. LaQue, F. L., Marine Corrosion - Causes and Prevention, John Wiley & Sons Inc., New York, 1975 3. R. Baboian, E. Blaine Cliver, E. Lawrence Bellante: The Statue of Liberty Res- toration. Proceedings of the Statue of Liberty - Today for Tomorrow Confer- ence. National Association of Corrosion Engineers, Houston, Texas, 1990 4 Einar Mattson: Electrokemi och korrosionsldra. Bulletin no. 100, Korrosionsinstitutet, Stockholm, 1987. v Control questions 1 The Statue of Liberty at Liberty Island, New York City, USA, was renovated during the 1980's in connection with the 100-year anniversary of the statue in 1986. The Statue of Liberty has an outer skin of copper sheets fastened to a steel frame by a special method. The copper skin was originally insulated from the stee! by means of asbestos impregnated with shellac. Discuss which corro- sion problems can be expected to appear, on the outside and inside, after 100 years’ exposure. 2. The galvanic series in sea water is discussed in this chapter. Explain what the galvanic series is and what practical value such a galvanic series may have for you in connection with the selection of materials. 3. Piping material for a sprinkler system for sea water on a platform is to be selected. The sea water has an average temperature of 15°C and it will be stagnant under pressure. Make a list of possible candidate materials. Describe which corrosion types may arise on the materials. State your reasons for the selection. 4 In connection with the selection of piping materials on board a fire fighting vessel at sea, a piping system in stainless steel was selected. Discuss whether corrosion problems can be expected after some time if the water used for fire fighting is sea water. BS