Metallurgical Factors Affecting Corrosion in Petroleum and Chemical Industries Dr. Eng. M. I.

Masoud, Associate Professor Industrial Engineering Department, Faculty of Engineering, Fayoum University Abstract: Humans have most likely been trying to understand and control corrosion for as long as they have been using metal objects. With a few exceptions, metals are unstable in ordinary aqueous environments. Certain environments offer opportunities for these metals to combine chemically with elements to form compounds and return to their lower energy levels. Corrosion is the primary means by which metals deteriorate. Most metals corrode on contact with water (and moisture in the air), acids, bases, salts, oils, aggressive metal polishes, and other solid and liquid chemicals. Metals will also corrode when exposed to gaseous materials like acid vapors, formaldehyde gas, ammonia gas, and sulfur containing gases. The production of oil and gas, its transportation and refining, and its subsequent use as fuel and raw materials for chemicals constitute a complex and demanding process. Various problems are encountered in this process, and corrosion is the major one. Since metals are the principal material suffering corrosive deterioration, it is important to develop a background in the principles of metallurgy to fully understand corrosion. The control of corrosion through the use of coatings, metallurgy, nonmetallic materials for constructions cathodic protection and other methods has evolved into a science in its own right and has created industries devoted solely to corrosion control. Metallurgical factors that affect corrosion are chemical composition, material structure, grain boundaries, alloying elements, mechanical properties, heat treatment, surface coating, welding and manufacturing conditions. Understanding these factors are of great importance to decrease and control corrosion problem in many industrial applications. 1. Introduction: Corrosion is the destructive attack of a material by reaction with its environment. The serious consequences of the corrosion process have become a problem of worldwide significance. In addition to our everyday encounters with this form of degradation, corrosion causes plant shutdowns, waste of valuable resources, loss or contamination of product, reduction in efficiency, costly maintenance, and expensive over design; it also jeopardizes safety and inhibits technological progress. Corrosion control is achieved by recognizing and understanding corrosion mechanisms, by using corrosion- resistant materials and designs, and by using protective systems, devices, and treatments. Major corporations, industries, and government agencies have established groups and committees to look after corrosion-related issues, but in many cases the responsibilities are spread between the manufacturers or producers of systems and their users. This study will focus mainly on the metallurgical factors and how it can affect corrosion of materials and alloys. From a purely technical standpoint, an obvious answer to corrosion problems would be to use more-resistant materials. In many cases, this approach is an economical alternative to other corrosion control methods. Corrosion resistance is not the only property to be considered in making material selections, but it is of major importance in the chemical and petroleum industries. The choice of a material is the result of several compromises. [1-7] For example, the technical appraisal of an alloy will generally be a compromise between corrosion resistance and some other properties such as strength and weldability.

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The final selection will be a compromise between technical competence and economic factors. In specifying a material, the task usually requires three stages: 1. Listing the requirements 2. Selecting and evaluating the candidate materials 3. Choosing the most economical material. Since metals are the principal material suffering corrosive deterioration, it is important to develop a good background in the principles of metallurgical variables to fully understand corrosion and its preventions. [5-8] 1.1. Corrosion Theory: Corrosion specifically refers to any process involving the deterioration or degradation of metal components. The best known case is that of the rusting of steel.

The corrosion process (anodic reaction) of the metal dissolving as ions generates some electrons, as shown here, that are consumed by a secondary process (cathodic reaction). These two processes have to balance their charges. The sites hosting these two processes can be located close to each other on the metal's surface, or far apart depending on the circumstances. This simple observation has a major impact in many aspects of corrosion prevention and control, for designing new corrosion monitoring techniques to avoiding the most insidious or localized forms of corrosion.

Corrosion processes are usually electrochemical in nature, having the essential features of a battery. When metal atoms are exposed to an environment containing water molecules they can give up electrons, becoming themselves positively charged ions provided an electrical circuit can be completed. This effect can be concentrated locally to form a pit or, sometimes, a crack, or it can extend across a wide area to produce general wastage. Localized corrosion that leads to pitting may provide sites for fatigue initiation and, additionally, corrosive agents like seawater may lead to greatly enhanced growth of the fatigue crack. Pitting corrosion also occurs much faster in areas where microstructural changes have occurred due to welding operations. Corrosion is the disintegration of metal through an unintentional chemical or electrochemical action, starting at its surface. All metals exhibit a tendency to be oxidized, some more easily than others. [8-10]

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1. oxide scales ( continuous or broken). the energy required to release the metals from their original compounds. [11] Following the different factors affecting corrosion: 1. 3. The amount of energy required and stored up varies from metal to metal. especially if these are variable over a surface. [11. Forms of Corrosion and its Analysis: Destruction by corrosion takes many forms depending on the nature of the metal or alloy. 12] 1. the nature of the corrosive medium. Time Factor Stress corrosion cracking of mild steels in nitrate solutions and crack velocity increases by the effect of high temperature. Material factor. called ores. steady or cyclic). Why Metals Corrode: The driving force that makes metals corrode is a natural consequence of their temporary existence in the metallic form. 6.3. built-in crevices. Temperature Factor. velocity of movement. It is relatively high for such metals as magnesium. Stress Factor. the presence of inclusions or other foreign matter at the surface. porous or semi-porous deposits on surfaces. the homogeneity of its structure.1. Geometry Factor 5. temperature. and iron and relatively low for such metals as copper and silver.2. A lesson hard to learn is that corrosion usually will be lessened or prevented by avoiding unnecessarily high temperatures. Environmental Factor. the incidental environmental factors such as the presence of oxygen and its uniformity. 4. 2. and such other factors as stress( residual or applied. it is necessary for them to absorb and store up for later return by corrosion. Fig. aluminum. galvanic effects between dissimilar metals and the occasional presence of “stray” electrical current from external sources. To reach this metallic form their occurrence in nature in the form of various chemical compounds. [5] 3 . Chart of different corrosion modes in petroleum and chemical industries.

refining and oil & gas industries. Metallurgical Factors Affecting corrosion: The structure of metals and alloys is of decisive importance in determining their corrosion characteristics which cannot.Figure (1) represents a chart of failure modes distributions in chemical and petroleum industries. localized corrosion. In those situations where the component would not have failed without the action of the corrosion. In an effort to better understand the general sources of plant failures a failure analysis company decided to look at the last three years' projects to determine the major failure contributors. [5] Studies of failure analysis are particularly strong in the chemical processing. 10] 2. be discussed without the use of metallurgical terms. coatings. [5. weld corrosion. sulfide inclusions in pure iron have a marked tendency to 4 .e. There were a total of 131 analyses and we list the primary failure mechanisms below: 23 Corrosion 57 Fatigue 15 Wear 17 Corrosion fatigue 19 Overload total = 131 18% 44% 11% 13% 15% Note: In defining these five categories there is the possibility of confusion between corrosion fatigue and fatigue.. For example of these factors. alloys. intergranular corrosion. there was cyclic loading but it was not severe enough to cause cracking without corrosion.6] Corrosion failure analysis involves metallurgical investigations of components. Human Error as a Factor of Corrosion Failures: The depth of the analysis into the roots of the failure is the key to accurately unearthing all of the failure sources. specifications Bad inspection Human error Poor planning and coordination Other Unforeseeable 36 16 10 12 14 4 8 This data set indicates that only 8% of corrosion failures are unforeseeable. metals. In other words 92 % of the corrosion failures could be preventable!?! [5. fatigue & corrosion fatigue. hydrogen embitterment and hydrogen sulfide cracking. 8. stress corrosion cracking. The practice was to assign fatigue as the mechanism in those cases where the component would have eventually failed and corrosion was not needed to affect the failure. therefore. i. Failure mechanisms evaluated usually include. 10] According to this study. material or process Lack of. 1. general corrosion. equipment.4. 8. misapplication of the particular metal and mechanical failure. fretting & wear. [2. the cause was listed as corrosion fatigue. linings and structures due to corrosion. environmental degradation and abuse. the attribution of responsibility for corrosion failures investigated by a large US based chemical company was broken down into the following: Lack of proving: new design. or wrong.

This will cause high corrosion possibility. The vacancy. the influence of impurities. In addition. 2. [9] Some fundamental metallurgical concepts are presented in this section: 2.react in even mild corrosive environments. in this condition the material is somewhat more reactive in electrochemical environments. Fig.) have a remarkable effect on the corrosion resistance of the materials. interstitial atoms and large lattice disturbance called dislocations. the grains are deformed and the grain structure is completely disrupted. Also heavily deformed material by plastic deformation at room temperature (cold worked. Material factors controlling corrosion failure. Normally. etc. grain boundaries and differences in grain orientation also may result significantly different electrochemical reactivates in many metals and alloys. These defects may be vacancies caused by the absence of atoms in the crystal. cold rolled. but in reality there are variations in the structure caused by crystalline defects. The large numbers of triangular corrosion pits are a result of electrochemical attack due to the stress 5 . inclusions. whereas dislocations are line defects affecting a much greater volume of the crystal. Each of the mentioned imperfections can produce highly localized differences in electrochemical behavior and corrosion resistance of the material as well. The crystal structure assumed to be perfect in three dimensions. Effect of Crystal Structure Defects and Phases on corrosion: On a smaller scale the differences in sub-microscopic characteristics of metals must be considered. In corroding environment (such as in petroleum and/or chemical industries) these areas are usually more anodic than the surrounding matrix. [9] In highly deformed metals. the impurity atom and interstitial atom are point defects. [18] Figure (2) shows some metallurgical factors that can affect corrosion failure of metals and alloys. impurity atoms of different sizes. cold drown.1.

Typical microstructure of 0. multiphase materials present a problem from the corrosion standpoint because the two phases may have marked differences in electrochemical characteristics. 28] 6 . stress corrosion cracking of brass. size. These materials are not truly corrosion resistant under all conditions. [24-26] The properties of steel or any multiphase material depend greatly on the relative physical and structural characteristics (amount. In fact. distribution. 27. Although an alloys resistance to corrosion is very important. useful.4%C steel. high purity metals generally have low mechanical strength. Alloying by itself has produced a number of materials which have improved corrosion resistance compared to high purity metals. However. Ferrite Fig. hence they are rarely used in engineering applications. stainless steel and high strength steel. These impurities and imperfections are inherent cause of corrosion in aggressive environment. [14. the existence of more than one phase in an alloy usually results in poorer corrosion resistance than the equivalent single phase materials. as well as economically. 3.field around dislocation. Figures (3 and 4) shows multi phase steel alloys of different carbon contents. The shape of the pit is related to the orientation of the grain to the corroded surface. [19-23] Metals listed as pure or commercially pure. they may be subjected to catastrophic failure as. intergranular attack of sensitized stainless steel. actually contain a variety of impurities and imperfections. In many cases. It has been shown that. the tendency for a metal to react in electrochemical environments reduces proportionality. However. as purity increases. therefore to work with metallic materials which are stronger and which are usually formed from a combination of several elemental metals. this factor is sadly neglected in the aim to improve the mechanical properties. [14] In general. etc. It is necessary. some two-phase alloys have small electrochemical differences and excellent corrosion resistance and others develop a protective film which results in improved corrosion properties for both phases. revealed ferrite and pearlite. The common alloys are those which have a good combination of mechanical. shape and strength) of the various phases in the alloy. physical and fabrication qualities which tend to make them structurally. It is possible that one phase will be selectively attacked in a corrosive environment.

sufficient diffusion cannot occur and non-equilibrium variations results. 29-32] 2. [14] 2. It is possible also to determine the approximate temperature for homogenization annealing. That is its metallurgical processing using heat treatment to transform or anneal the structure of the metal or alloy. this information if used wisely.These are examples of some metallurgical factors affecting corrosion. Annealing. In some cases it is possible to reduce major chemical differences in a cored structure by reheating the alloy and holding it for a relatively long time at temperature just below the solidus line. 4. Fig. Cementite precipitation at austenitic boundaries. 34] 7 . This allows diffusion to occur more rapidly and assists in homogenization of the alloy.2. Consider a single grain of material rapidly solidified from a liquid. [5. is very important heat treatment process usually done to produce one of two effects affecting corrosion resistance of the material: [5. can be a tremendous help in obtaining the maximum in corrosion resistance from alloys. 33. This variation in chemical composition from the interior to the exterior of a grain is termed "coring". Effect of Castings Composition Inhomogeneity on Corrosion: It is very important to understand the casting inhomogeneous chemical composition as a result of non-equilibrium solidification.3. remaining austenite is transformed into pearlier (1. If the cooling of the cast alloy is rapid. Effect of Heat Treatment on Corrosion Behavior: Many of the final mechanical properties and the corrosion resistance of a material can be related to its heat treatment. It is important to mention that many cases of intergranular corrosion result from this type of chemical inhomogeneity. A variation in composition will exist from the interior to the surface of the grain because diffusion is not fast enough. This inhomogeneity is very important in determining the corrosion characteristics of many cast alloys. Cored structures generally have widely different corrosion characteristics and actually have a built in electrochemical cell.3 C %).

Aluminum alloys do not readily form this protective oxide. copper and some forms of stainless steel. Often impurities or atoms of alloying metals migrate to these imperfections to cause an even greater change in the electrochemical characteristics of these defects. nickel. In the precipitation hardening alloy. In various corrosive environments.First. Martensitic Transformation and Corrosion: Quenching of steel from Gamma region (austenite phase) results in the formation hard and brittle phase called martensite (hard and brittle phase). This annealing treatment to a great extend reduces the corrosion tendency of the materials and alloys. homogenization of cast alloys which may exhibit chemical inhomogeneity (coring). this results in preferential corrosion adjacent to and at grain boundaries. Generally.4. To develop this protection on alloys. This explains the extremely good corrosion resistance of aluminum. Residual stresses and cold work in deformed metals reduces its resistance to general corrosion.6] Aluminum. It is well known that pure aluminum forms a thin film of aluminum oxide which provides a very effective barrier to environmental attack. best combination of strength and toughness can be obtained after tempering at intermediate temperature. Chemical inhomogeneity of an alloy cause reduction in its mechanical properties. and second. reducing in corrosion resistance often occurs. [5. magnesium. a thin layer of pure aluminum is often clad to the outer surface. Homogenizing anneal is important for chemical homogeneity of an alloy by diffusion (movement of atoms in the solid state). [38-40] 8 . If possible hardened steels should be protected in corrosive environment by some form of surface treatments ranging from simply painting or lubricating to special plating or coating procedures. remove residual stress and cold work effects in deformed metals. Just as a homogenization anneal is required to produce more uniform chemical composition. [34-37] Because the cladding is only a few mils thick. it is possible that deterioration of the resistance to corrosion of clad material can occur due to improper heat treatment. the precipitated phase may cause a so-called denuded zone adjacent to the grain boundaries that is more subject to corrosion attack. full annealing tends to produce a more uniform crystal structure. This layer develops a protective surface oxide. A good example of the problem encountered when using a heat treated unprotected high strength steel in the so-called sucker rods used in the oil well pumping. However. these areas of high dislocation density are usually subjected to pitting corrosion. an increase in strength and hardness due to heat treatment is accompanied by decreased corrosion resistance. Deformation decreases corrosion resistance basically because it increases dislocations in the cold deformed metals. When salt water or hydrogen sulfide solutions are encountered. with fewer defects leading to better corrosion resistance. when alloyed with certain elements can be strengthened by age hardening or precipitation hardening treatments. Therefore. the corrosion resistance of the important aluminum age hardening alloys is not as good as pure aluminum with its atmospherically oxidized surface. stress corrosion cracking occurs. in addition. It is also possible to use treatments to develop thick oxide layers directly on the alloy. Thus annealing a cold worked metal may result in a decrease in dislocations and important improvements in the corrosion resistance. little or no loss of the mechanical properties of the alloy is noted. [36-38] 2. This termed intergranular corrosion.

especially when the operating conditions become aggressive. fittings. are most commonly used at temperatures up to 650°C. oxidation and sulfidation resistance. [11-15] A mechanical property can be defined best as a measure of the ability of a material to withstand the mechanical forces applied to it. Unfortunately. valves. Use of alloying additions. compromises must frequently be made to realize the best performance of the selected material. Corrosion Control by Application of Metallurgical principals: It is possible to reduce or prevent corrosion by application of the following metallurgical principals: 1. The selection criteria used by materials engineers in choosing from a group of materials includes a list of qualities that are either desirable or necessary. Lead in zinc die cast alloys also has a marked effect on the corrosion characteristics of the material. [32] Although plan carbon steel often used in applications up to 482 to 516°C. Thus. Knowledge of the metallurgical history of the used material A high purity metal has better general corrosion resistance and a reduced tendency to pitting. 9 . 4. [12-15] 3. with additions consisting primarily of chromium (0. Corrosion Properties and Material Selection: The corrosion engineer is often required to consider one or more properties in addition to corrosion resistance and strength when selecting a material. the ability of a metal or alloy to withstand mechanical loading often is used as the sole criterion in material selection. One of the best examples of improvement of corrosion resistance of a material is found in results achieved by reducing the sulfur content of plain carbon steels. these low-alloy steels have inadequate corrosion resistance to many other elevated temperature environments for which more highly alloyed. For applications for which carbon or low-alloy steels are not suitable. it precipitates at the grain boundaries and produces an increased tendency for intergranular corrosion. piping. Use surface coatings. the most common choice of material is from within the 18Cr-8Ni austenitic group of stainless steels.5 to 1%). A wide variety of iron.2. Use of high purity material. higher strength. is the mechanical property the most important consideration. 5. Only if the structure is protected from all environmental effects. The problem of material selection in petroleum and chemical industries is because. most of its use is limited to 316 to 343°C due to loss of strength and susceptibility to oxidation and other forms of corrosion at higher temperature.and nickel-based materials are used for pressure vessels. The limits of their mechanical properties greatly reduce their application possibilities.5. Corrosion attack on a steel greatly reduced when its sulfur level is low. Ferritic alloys. However. Ni-Cr-Fe alloys are required. the optimum properties associated with each selection criteria can seldom all be found in a single material. result in their being the material of choice. The most common of these is plain carbon steel.002%. Effective heat treatments. If the lead exceeds 0. 3. 2. and other equipment in chemical industries. These alloys and the 18Cr-12Ni stainless steels are favored for their corrosion resistance in many environments and their oxidation resistance at temperatures up to 816°C.5 to 9%) and molybdenum (0. for example. and particular resistance to hydrogen. too often the relation of the metal to stress plus environment is neglected. Unfortunately. Their comparative cost.

Many alloys have a temperature range for aging in which they are not susceptible to intergranular corrosion. the addition of magnesium or chromium to aluminum alloys. Consequently. Impurities retained from the original extractive processes. the aging temperature for optimum mechanical properties of an alloy may reduce susceptibility to intergranular corrosion. For example: 1. The addition of magnesium or chromium changes the FeAl3 to a complex Al-Fe-Mn or Al-Fe-Cr compound whose potential now approaches that of the aluminum itself. the inclusions and imperfections introduced in casting and forming. In these alloys. However. Heat treatment of the surfaces to increase surface hardness of the material or improve the stability of surface films is important in resisting all types of corrosion but is particularly useful in improving fretting and erosion-corrosion resistance. [6. Corrosion resistance also may be improved by changing the electrochemical potential of the second phase in an alloy. 50] Heat treatment: It has been discussed later that it is possible to modify the structure of metals and alloys in many ways through heat treatment. 47-49] The intergranular sensitization of stainless steels due to the formation of chromium carbide at grain boundaries can be prevented using alloying additions. which are the basics of stainless steel corrosion resistance. 41-44] Alloy additions: It is possible to improve the corrosion resistance of certain alloys by specific alloying additions. Hot rolling steel results in scale formation which. Of course. High zinc brasses. greatly affects pitting and corrosion resistance. it is possible to add columbium or titanium which selectively ties up the carbon as carbides. [50] Surface coatings for corrosion control: Because the corrosion reactions occur at metalenvironment interface. 10 . [45] It has been shown recently that stress relief greatly improves the resistance of 300 Series stainless steels to stress corrosion. Thus a thorough knowledge of the background of the material is important. eliminating chromium carbide formation and the sensitization of the alloys as well. Age-hardening heat treatments also have great effect on the corrosion resistance of alloys. serves to produce corrosion pit initiation sites. [18-20. Relation of metallurgical history and corrosion: Nearly all forms of metal deterioration are dependant upon the metallurgical history of the material. of course. if not properly removed by pickling. higher sulfur resulted and. the intermetallic compound. FeAl3. 427°C. At or above this concentration.03% carbon. Often it is important to sacrifice some mechanical properties in order to improve corrosion resistance. corrosion resistance will be lower. inorganic and organic materials. The most notable is the addition of chromium to iron in amounts of 12% or more. 2. plus structure variations due to heat treatment all alter the corrosion stability of metals and/or alloys.Stainless steel 300L has a maximum limit of 0. it is logical that the interpositions of barriers between the substrate and the environment would influence the corrosion rate. In these alloys. the stress relieving must be below the temperature of sensitization. For example. susceptible to stress corrosion in the cold working state. the pitting tendency is greatly reduced. Various types of barriers are commonly used for corrosion control including a wide range of metals. particularly to nickel and iron base materials increases their high temperature oxidation resistance. [6. The addition of chromium. a passive film o chromium-iron oxide is formed on the surfaces. This reduces the possibility of sensitization as a result of welding or/and heat treatment. also have been protected effectively by stress relief. When steels were made in acid open hearth.

It is not necessary to chemically treat stainless steels to achieve passivity. as oil filed and chemical industries. when steels are treated to 11 . surface condition. depending on the quantity of alloying elements. severe pitting of the steel may occur if large amounts of millscale are present on the surface. and fabrication procedures. corrode in many media including most outdoor atmospheres. 53] 5. usually termed millscale. all of which may change the thermodynamic activity of the surface and thus dramatically affect the corrosion resistance. These differences show up in the rate of metal lost due to rusting. [6. Stainless steels are mainly used in wet environments. 52] 4. Stainless Steel Corrosion: Stainless and heat resisting steels possess unusual resistance to attack by corrosive media at atmospheric and elevated temperatures. and cost. Rapid cooling or quenching through this range avoids sensitization. The passive film forms spontaneously in the presence of oxygen. Slow cooling of regular 300 Series stainless steel through the 760°C to 427°C temperature range sensitizes it to intergranular corrosion. and can also extend paint life by decreasing the amount of corrosion underneath the paint. In air. but also of heat treatment. the presence of millscale on the steel may reduce the corrosion rate over comparatively short periods.3% copper to carbon steel can reduce the rate of rusting by one quarter or even by one half. tightly adhering rust scale is a factor in lowering the rate of attack. In some circumstances. All steels and low-alloy steels rust in moist atmospheres. Austenitic steels are more or less resistant to general corrosion. Formation of a dense.3. chromium and nickel have all been shown to improve resistance to atmospheric corrosion. Resistance to pitting and crevice corrosion is very important if the steel is to be used in chloride containing environments. the most commonly used metals. crevice corrosion and pitting. [51. Usually they are selected not for their corrosion resistance but for such properties as strength. Most frequently. 52] 4. The rate of rusting will usually be higher in the first year of atmospheric exposure than in subsequent years. In water. [6. [51. [54] Corrosion resistance of stainless steels is a function not only of composition. Thus knowledge of the basic principles of metallurgy and an understanding of the metallurgical history of the material is extremely important to the final behavior of the metal in service especially from the corrosion standpoint of view. The improvement may be sufficient to encourage use without protection. The elements copper. 53] During hot rolling and forging the steel surface is oxidized by air and the scale produced. the addition of 0. Resistance to pitting and crevice corrosion typically increases with increasing contents of chromium. the steels become increasingly resistant to aggressive solutions. and are produced to cover a wide range of mechanical and physical properties for particular applications. but over longer periods the rate tends to rise. and will increase significantly with the degree of pollution and moisture in the air. ease of fabrication. The higher nickel content reduces the risk of stress corrosion cracking (SCC). phosphorus. Residual stresses due to cold working of an alloy or unequal cooling of welded structures can lead to stress corrosion. With increasing chromium and molybdenum contents. Steel Corrosion: Iron and steel. molybdenum and nitrogen.

1. which it does almost immediately. Problems of Welding Stainless Steel: To fabricate complex equipments and structures for modern industries it is necessary to produce structurally sound joint using different welding procedures. [56] 5. which have a higher affinity than does chromium for carbon: hence carbides of these elements tend to form instead of chromium carbides. For example. The local loss in corrosion resistance arises because the chromium is crucial in promoting the formation of a Cr-rich passive film on the surface of stainless steels. Stainless Steel Weld Decay: This type of intergranular corrosion can occur in the heat-affected zone of welded components and also in cast components of stainless steel due to precipitation.2. 2. Pickling and Passivation of Stainless Steel: Stainless steel can corrode in service if there is contamination of the surface. thus avoiding the Cr-depletion problem: such steels are usually termed “stabilised stainless steels” b. welding can cause intergranular sensitization of stainless steels. [44] 12 .improve passivity (passivation treatment). Produce high stress in the adjacent to weld which greatly reduce corrosion resistance in these zones. Cause secondary precipitation. [6. [54] 5. sensitization can occur in austenitic stainless steels and this can lead to rapid deterioration and destruction especially in high corrosive atmosphere like petroleum and chemical industries. surface contaminants are removed by pickling to allow the passive film to reform in air. Specification of a stainless steel containing a small amount of either titanium or niobium. In the heat affected zone to welds (HAZ).03%).3. Consequently the usual strategy in combating weld decay is by the choice of stainless steel with either of the two following features: a. for instance the “316” grade of steel (18%Cr/10Ni/2. of chromium carbides at the grain boundaries (and hence loss of chromium in the immediately-adjacent zone). it may be necessary to use a detergent or alkaline clean before pickling or passivation.5Mo) is designated as “316L” when its carbon content has been limited in this way. Both pickling and passivation are chemical treatments applied to the surface of stainless steel to remove contaminants and assist the formation of a continuous chromium-oxide. Through the application of heat. Pickling and passivation are both acid treatments and neither will remove grease or oil. If the fabrication is dirty. passive film. Such low-carbon grades of stainless steel are often designated by a “L” in their code. 3. The susceptibility to weld decay can be counteracted by carrying out a suitable post-weld heat treatment to restore a uniform composition at the grain boundaries but this is clearly often not a practicable proposition. Induce phase transformations. welding may: 1. Specification of a stainless steel with low carbon content (< 0. this will clearly decrease the likelihood of carbide formation in the steel. 54] 5. during cooling.

The grain boundaries are susceptible to intergranular corrosion and are anodic to the surrounding grains. [45] 5. These alloys when heated in 427 to 760°C form chromium carbide. this often can result in high tensile stresses. Figure (5) is schematic illustration of stainless steel intergranular corrosion. for optimum corrosion resistance. it is important to maintain homogeneity between the weld and base metal. The other basic metallurgical considerations discussed in this survey should be considered in welding. [36] Sensitized stainless steels can deteriorate completely in the specific hours in strongly acid solutions. The situation with buried pipelines is a good example of such complexity. The principals of heat treatment applicable to each material must be considered to produce the more effective combination of mechanical properties and environmental stability. The problem itself can be quite complex. It is important to stress relieve welds exposed to environments that could cause stress corrosion cracking. [41-44] Fig.4. Upon solidification. In addition. For example. Under these conditions. Problems Involved in Heat Treatment of Stainless Steel: Stainless steels. a large variation of thermal expansion occurs between the solidifying molten metal pool and the base metal. the highly stressed areas are subjected to stress corrosion cracking in corrosive environment. so weld filler-metals should be used which are chemically and electrochemically similar to the base metals. Thus the chromium near the grain boundaries is tied up as carbide and no longer can act as a deterrent to corrosion. 13 . any phase transformations which could occur in welding must be considered in estimating the corrosion stability of welded structures. The required tensile stresses may be in the form of directly applied stresses or in the form of residual stresses. Stress Corrosion Cracking (SCC): Stress corrosion cracking (SCC) is the cracking induced from the combined influence of tensile stress and a corrosive environment. these carbides forms only at the grain boundary.During welding. particularly the 300 Series are subject to a heat treating effect called "sensitization". 5. Intergranular corrosion occurs in stainless steel. [44] 6.

6. 14 . [6] Macroscopically. heat treatment. [6] Fig. [6] Cold deformation and forming. Figure (6) micrograph illustrates intergranular SCC of an heat exchanger tube with the crack following the grain boundaries. The residual stresses set up as a result of welding operations tend to approach the yield strength. SCC is classified as a catastrophic form of corrosion. SCC fractures have a brittle appearance. Chloride stress corrosion cracking in austenitic stainless steel is characterized by the multi-branched "lightning bolt" transgranular crack pattern. (7). as the detection of such fine cracks can be very difficult and the damage not easily predicted. The magnitude and importance of such stresses is often underestimated. 7. welding. The micrograph of SCC in a 316 stainless steel chemical processing piping system was shown in Fig.Fig. Intergranular SCC occurs in a heat exchanger (X500). SCC of 316 stainless steel chemical processing piping system (X300). machining and grinding can introduce residual stresses. Stress corrosion cracking usually occurs in certain specific alloy-environment-stress combinations.

45] Figure 8 Stress corrosion crack propagation. Pipeline Stress Corrosion Cracking: Over 98% of pipelines are buried. covering a range in color. soil movements/instability and third party damage. stresses and material. Control of Stress Corrosion Cracking: The most effective means of preventing SCC are: 1) design properly with the right materials. once in place they are subjected to environmental abuse. [5-7] In an ideal world a stress corrosion cracking control strategy will start operating at the design stage. texture. Coating types such as coal tar. 4) and avoid stagnant areas and crevices in heat exchangers where chloride and hydroxide might become concentrated. and oxygen. No matter how well these pipelines are designed. No single characteristic has been found to be common to all of the soil samples. the limitation of stress and the 15 . Stress Corrosion Crack Propagation Rate: Stress corrosion cracks (shown in Fig. Propagated SCC of pipeline is shown in Fig. (8). [6] 6.6.2. constructed and protected. Low alloy steels are less susceptible than high alloy steels. Fusion bonded epoxy hasn't shown susceptibility to SCC. asphalt and polyethylene tapes have demonstrated susceptibility to SCC. Environment is a critical causal factor in SCC.1. (8)) propagate over a range of velocities from about 10-3 to 10 mm/h. [6. inherent mill defects. but they are subject to SCC in water containing chloride ions. or the crack tip strain rate defines the extent of corrosion or hydrogen ingress into the material. Cyclic loading is considered a very important factor. coating disbandment. and pH. [6] 6. chlorides. 2) reduce stresses. High-pH SCC failures of underground pipelines have occurred in a wide variety of soils. depending upon the combination of alloy and environment involved. Their geometry is such that if they grow to appropriate lengths they may reach a critical size that result in a transition from the relatively slow crack growth rates associated with stress corrosion to the fast crack propagation rates associated with purely mechanical failure. and will focus on the selection of material. In pipelines SCC occurs due to a combination of appropriate environment.3. [6] Loading is the next most important parameter on SCC. 3) remove critical environmental species such as hydroxides. external damage.

[32] 16 . subsequent SCC problems can be avoided. partial stress relief around welds and other critical areas may be of value.3. Intergranular corrosion is localized attack along the grain boundaries. or in a zone adjacent to it that has lost an element necessary for adequate corrosion resistance. Residual stresses can be relieved by stress-relief annealing. thus making the grain boundary zone anodic relative to the remainder of the surface. [12] For large structures. it is not always quite that simple. and this is widely used for carbon steels. and expert advice is advisable if this approach is adopted. [17] 6. or immediately adjacent to grain boundaries. Some environments. of course the materials that are resistant to SCC will almost inevitably be the most expensive. entire grains may be dislodged due to complete deterioration of their boundaries. Intergranular Corrosion: The microstructure of metals and alloys is made up of grains. In any case the mechanical properties of the structure will be seriously affected. This is not usually feasible for working stresses. or at least reduce it below the threshold stress for SCC. such as high yield strength. while the bulk of the grains remain largely unaffected. Unfortunately. for which full stress-relief annealing is difficult or impossible. can be very difficult to reconcile with SCC resistance (especially where hydrogen embrittlement is involved). The attack is usually related to the segregation of specific elements or the formation of a compound in the boundary.1.2.3. This form of corrosion is usually associated with chemical segregation effects (impurities have a tendency to be enriched at grain boundaries) or specific phases precipitated on the grain boundaries. Control of Environment: One of the most direct ways of controlling SCC through control of the environment is to remove or replace the component of the environment that is responsible for the problem. The skill of the engineer then lies in selecting the strategy that delivers the required performance at minimum cost: [6] 6. such as high temperature water are very aggressive. Mechanical requirements. one method of control is to eliminate that stresses. Selection and Control of Material: The first line of defense in controlling stress corrosion cracking is to be aware of the possibility at the design and construction stages. it is relatively rare for this approach to be applicable. and will cause SCC of most materials. Corrosion then occurs by preferential attack on the grain-boundary phase.3. separated by grain boundaries. in a severe case of grain-boundary corrosion. By choosing a material that is not susceptible to SCC in the service environment and by processing and fabricating it correctly. Control of Material Stress: As one of the requirements for stress corrosion cracking is the presence of stresses in the components.control of the environment. this must be done in a controlled way to avoid creating new regions of high residual stress. Unfortunately. but it may be possible where the stress causing cracking is a residual stress introduced during welding or forming. 25] 6. However.3. The attack usually progresses along a narrow path along the grain boundary and. Finally. [6. [23] 7.

Contrary to a pure mechanical fatigue.A classic example is the sensitization of stainless steels or weld decay. but not branched. [6. In austenitic stainless steels. These carbides build up next to the weld bead where they cannot diffuse due to rapid cooling of the weld metal. Control of corrosion fatigue can be accomplished by either lowering the cyclic stresses or by various corrosion control measures. the failure can take place at even lower loads and after shorter time. 9. The problem of knife-line attack can be corrected by reheating the welded metal to allow diffusion to occur. Much lower failure stresses and much shorter failure times can occur in a corrosive environment compared to the situation where the alternating stress is in a non-corrosive environment as shown in Fig. there is no fatigue limit load in corrosion-assisted fatigue. [6] The fatigue fracture is brittle and the cracks are most often transgranular. [6. down to 75 to 25% of the fatigue strength in dry air. Reheating a welded component during multi-pass welding is a common cause of this problem. upon which corrosion is accelerated. [11] No metal is immune from some reduction of its resistance to cyclic stressing if the metal is in a corrosive environment. (10) reveals a primary corrosion-fatigue crack that in part has been widened by a secondary corrosion reaction. 12] 8. In a corrosive environment the stress level at which it could be assumed a material has infinite life is lowered or removed completely. 11] 17 . Even relatively mild corrosive atmospheres can reduce the fatigue strength of aluminum structures considerably. Effect of corrosion atmosphere on the fatigue failure stress. titanium or niobium can react with carbon to form carbides in the heat affected zone (HAZ) causing a specific type of intergranular corrosion known as knife-line attack. The corrosive environment can cause a faster crack growth and/or crack growth at a lower tension level than in dry air. (9) [6] Fig. as in stresscorrosion cracking. leaving these areas vulnerable to corrosive attack in certain electrolytes. Corrosion Fatigue: Corrosion-fatigue is the result of the combined action of an alternating or cycling stresses and a corrosive environment. Chromium-rich grain boundary precipitates lead to a local depletion of Cr immediately adjacent to these precipitates. If the metal is simultaneously exposed to a corrosive environment. The fatigue process is thought to cause rupture of the protective passive film. The picture shown in Fig.

the cracking phenomenon is often termed “sulphide stress cracking (SSC)”.Fig. baking heat treatment to expel any hydrogen is employed b. If the presence of hydrogen sulfide causes entry of hydrogen into the component. Hydrogen Embrittlement: This is a type of deterioration which can be linked to corrosion and corrosion-control processes. in particular. in welding. [6. an event that can seriously reduce the ductility and load-bearing capacity. Hydrogen embrittlement occurs in a number of forms but the common features are an applied tensile stress and hydrogen dissolved in the metal. cathodic protection. and electroplating. Hydrogen embrittlement does not affect all metallic materials equally. cracking failures can often be thought of as a type of stress corrosion cracking.1. It involves the ingress of hydrogen into a component. By some manufacturing operations such as welding. 10. Sources of Hydrogen: Sources of hydrogen causing embrittlement have been encountered in the making of steel. In this situation. Hydrogen entry. As a by-product of corrosion reaction such as in circumstances when the hydrogen production reaction acts as the cathodic reaction since some of the hydrogen produced may enter the metal in atomic form rather than be all evolved as a gas into the surrounding environment. 44] 9. Hydrogen may be produced by corrosion reactions such as rusting. 17] 18 . 17] a. electroplating. Examples of hydrogen embrittlement are cracking of weldments or hardened steels when exposed to conditions which inject hydrogen into the component. and pickling. the obvious pre-requisite of embrittlement can be facilitated in a number of ways summarized below: [6. cause cracking and catastrophic brittle failures at stresses below the yield stress of susceptible materials. in storage or containment of hydrogen gas. Effect of corrosion atmosphere on the fatigue failure stress. and related to hydrogen as a contaminant in the environment that is often a by-product of general corrosion. in processing parts. Presently this phenomenon is not completely understood and hydrogen embrittlement detection. if a material subject to such operations is susceptible to hydrogen embrittlement then a final. [6] 9. seems to be one of the most difficult aspects of the problem. [6.

It is believed that. If stress induces cracking under these conditions. There are many metallurgical factors that affect corrosion as. Texas. The cracking of martensitic and precipitation hardened steel alloys is believed to be a form of hydrogen stress corrosion cracking that results from the entry into the metal of a portion of the atomic hydrogen. 17] Summary: Corrosion control is very important in all around us for many industrial applications as well. using non-metallic materials. NACE Basic Corrosion Course. the corrosion engineer must understand the basics and fundamentals of metallurgy very well. a few pertinent references which give additional details on the various metallurgical phenomena are cited in the Bibliography. Hydrogen embrittlement is a primary reason that the reactor coolant is maintained at a neutral or basic pH in plants without aluminum components. corrosion fatigue. H. 19 . tending to gather at inclusions or other lattice defects. mechanical properties. surface coating. Because corrosion of metal is so deeply involved in the basic principals of metallurgy. Houston. NACE Basic Corrosion Course. Texas. chemical composition. [6. Thus. brittle failure can occur. the hydrogen atoms are absorbed into the metal lattice and diffused through the grains. the path is transgranular. this work needs more study and investigations in the future. LaQUE. petroleum and chemical industries revealed many corrosion problems as. F. Hopefully. material structure imperfections and defects. processing. treatment and machining. material structure. There are several methods for corrosion control first. grain boundaries. Robert F. alloying elements. etc. 1970. At high temperatures. Many of the corrosion failure problems can be prevented by a proper attention from the early stage of material manufacturing. 37] If the metal is under a high tensile stress. welding and manufacturing conditions and stresses (residual or applied). corrosion inhibitors. 1970. This because the very corrosive atmosphere in these kind of industries.9. It is concluded from this study that metallurgical factors is the milestone of the right way for minimizing corrosion to be as less as possible in the most corrosive environment industries. to form methane gas. Peacock. Texas. G. M. Houston. 1970. which is alloyed with the iron. Houston. Understanding these factors is of great importance to minimize and control corrosion problem in many industrial applications.2. this study can help the corrosion engineer to have enough knowledge and background of metallurgical concepts that help for corrosion prevention and control. References: 1. [6. metal coating. Fontana and J. NACE Basic Corrosion Course. stress corrosion cracking. Since the environment play an important role in materials corrosion. 2. . The methane gas is not mobile and collects in small voids along the grain boundaries where it builds up enormous pressures that initiate cracks. heat treatment. At normal room temperatures. 3. cathodic protection. intergranular corrosion. Hydrogen Embrittlement of Stainless Steel: Hydrogen diffuses along the grain boundaries and combines with the carbon. pitting corrosion. L. proper material selection and design. Hochman. etc. All these corrosion failures are to great extent depend on the abovementioned metallurgical factors. the absorbed hydrogen tends to gather in the grain boundaries and stress-induced cracking is then intergranular.

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