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Thanks to Allah, that I had finished this project only by his guidance and will. Words cannot convey our sincere gratitude, deep Appreciation and thanks to: Dr. Moustapha Ibrahim Ahmed Salem Mansour For his close and keen supervision, creative comments, advice, sincere unlimited helpful assistance and continuous guidance along with his constructive suggestions, giving us too much of his busy time and efforts in performing this work.. Also, a special acknowledgment and appreciation is directed to MY FATHER & MOTHER For better or for worse, endured with cheer, patience, encouragement, and support and being a continuous source of moral inspiration during the period of this study.
1. Summary .......................................................................................................... 1 2. Introduction ..................................................................................................... 2 3. Theoretical Part ............................................................................................... 3 3.1.Corrosion Engineering ............................................................................ 3 3.2.Nature of Corrosion .............................................................................. 4 3.3.Definition of Corrosion ........................................................................ 5 3.4.Environments ........................................................................................ 6 3.5.Other definition of corrosion ................................................................ 7 3.6.Environments ........................................................................................ 9 3.7.Corrosion Theory ................................................................................ 10 3.8.Corrosion Reactions .............................................................................. 12 3.9.Chemical Factors:.................................................................................. 14 3.10.Water Composition: ............................................................................ 14 3.11.Dissolved salts ..................................................................................... 17 3.12.Dissolved Gases .................................................................................. 17 3.13.Combating Corrosion .......................................................................... 24 3.13.1.Select Proper Material .............................................................. 24 3.13.2.Proper Design ........................................................................... 27 3.13.3.Alter Environment.................................................................... 27 3.14.Crevice Corrosion ............................................................................... 29 3.15.Pitting corrosion .................................................................................. 31 3.16.Environmentally induced Cracking .................................................... 32 3.17.Nature of Corrosion............................................................................. 40 3.18.Polarization.......................................................................................... 44 3.19.Corrosion in Acids .............................................................................. 48 3.20.Metals and Alloys ............................................................................... 50
3.21.Costs of Corrosion............................................................................... 50 3.22.Literature survey ................................................................................. 52 4. Experimental Part ......................................................................................... 55 4.1.Apparatus .............................................................................................. 55 4.2.Materials used ....................................................................................... 57 4.3.Run calculations .................................................................................... 57 4.4.Procedures ............................................................................................. 57 4.5.Calibration curve ................................................................................... 57 4.6.Analysis calculations ............................................................................. 58 4.7.Analysis procedure ................................................................................ 58 4.8.Calibration curve ................................................................................... 58 4.9.Scanning for iron ions ........................................................................... 59 5. Results and discussion................................................................................... 61 5.1.Laminar flow ......................................................................................... 61 5.2.Turbulent flow ....................................................................................... 62 5.3.For galvanic corrosion with iron ........................................................... 63 6. Conclusion ...................................................................................................... 65 7. References ...................................................................................................... 66
1 . Summary The corrosion was determined experimentally using measuring of conc. of Cr (VI) method. The effect of flow rate was studied. This work is carried out at 30c.1. It was found that the corrosion rate increase with increasing flow rate for the corrosion of Copper in acidified potassium dichromate.
surface films and stresses. Introduction Corrosion is the destruction metals by interaction with the environment.2. 2 . inclusions and dissolve gasses. Among the metallurgical factors that influence rate of a given metal are composition. The environmental factors that influence the rate of corrosion are concentration. and voids. The corrosion of a metal is depending on the chemical nature of the metal and environment. internal structure& the nature of engineering application for which it used. internal stresses. electrochemical couples. It doesn’t occur also to plastics concrete and wood. Corrosion of Copper such other metals are a process of chemical reactions and takes place by loss or transfer of electrons. The electrochemical behavior theory now with over proposes that the corrosion of metals is largely accomplished by action of network of short-circuited electrolytic cells on the metal surface.
Most of the people then engaged in this field had chemical. and the ability to think and analyze an awareness of the importance of safety. Ignorance is the cause of many premature. physical. Corrosion Engineering Corrosion engineering is the application of science and art to prevent or control corrosion damage economically and safely. or metallurgical backgrounds. corrosion engineers must be well versed in the practices and principles of corrosion: the chemical. the corrosion engineer must select the method that will maximize profits. the nature of corrosive environments. unexpected. of prime importance. In solving corrosion problems. For example. computers. and expensive failures ignorance even by people who should know better.3. What this all means is that now there are hundreds of engineers in the field who have had a formal course in corrosion." In the past. Theoretical Part 3. common sense. a sense of organization. universities and colleges (including the author’s) offer formal courses in corrosion. and design. the availability and fabrication of materials. From only three in 1946. 3 . Corrosion Engineering is a popular textbook for these courses. now 65 U. relatively few engineers received educational training in corrosion. which is completely different. One definition of economics is simply "there is no free lunch.1. Fortunately this picture has changed. a solid feeling for economics. They also must have the usual attributes of engineers a sense of human relations. corrosion is often regarded as a "necessary evil" to be tolerated.S. and. metallurgical. electrical. and mechanical properties of materials: corrosion testing. In the past and even today. two vendors of sacrificial anodes describe their systems as anodic protection! Actually it is cathodic protection. integrity. In order to perform their function properly.
silicates. in which energy is supplied to the system in the form of chemical. in the case of zinc.3. For example. carbonates. are usually found in nature combined with non-metals as oxides. etc. sulphides. Hg and the Pt metals. and the acid solution of zinc sulphate can then be electrolysed (supply of electrical energy) to give a deposit of zinc metal at the cathode: ZnSO4 + H2O Zn + H2SO4 + ½O2 (Overall reaction) The overall reaction can also be written in the form of two half-reactions showing the cathodic reduction of zinc ions to zinc metal and the anodic oxidation of water to oxygen and acid (hydrogen ions): Cathodic reduction: Zn2+ + 2e Zn Anodic oxidation: H2O 2 H+ + ½O2 + 2 eIt should be noted that a similar process is used for electroplating zinc. which has a greater affinity for oxygen than the metal. and the process can be represented by the chemical reactions: 2 ZnO + C 2 Zn + CO2 2 Fe2O3 + 3 C 4 Fe + 3 CO2 Alternatively. with the exception of the noble metals Cu.2. the anodic reaction in this case is the reverse 4 .. Nature of Corrosion Metals. the oxides of zinc and iron can be reduced to the metal by using the chemical energy of carbon. Ag. are the stable form of the metal. To obtain the metal the ore (in which the compound of the metal. and since these have existed in the earth from time immemorial it follows that these compounds. or mineral. rather than the metal. is present in a suitable form and at a sufficient concentration for its conversion to the metal to be technologically and economically feasible) is subjected to a reduction process. the oxide can be leached from the ore by means of sulphuric acid. Au. but whereas in the extraction process an inert anode is used (frequently lead) a zinc anode is used in electroplating in order to ensure that the concentration of zinc ions is maintained fairly constant. electrical or thermal energy.
Definition of Corrosion Corrosion is defined as the destruction or deterioration of a material because of reaction with its environment. Sensitized 18-8 stainless steel is badly attacked in hours by polythionic acid. it tends to revert to its oxide Fe2O3. 5 . Some insist that the definition should be restricted to metals. Thus when iron is exposed to an aqueous environment containing dissolved oxygen. It is about 32 feet high and 2 feet in diameter. Indeed if metal extraction is regarded as the winning of a metal from its ores for a profit then corrosion is the converse process. loss of metal and loss of profit. and attack of a solid metal by another molten metal (liquid metal corrosion) are all considered to be corrosion. that it has been exposed mostly to arid conditions. deterioration of paint and rubber by sunlight or chemicals.e. For example. which corresponds in composition to the naturally occurring mineral lepidocrocite. but often the corrosion engineers must consider both metals and nonmetals for solution of a given problem.of equation of cathodic reduction. which will occur when it is exposed to the atmosphere or immersed in a natural water. 3. Corrosion can be fast or slow. It should be noted.3. however. the zinc metal being oxidized to zinc ions. Railroad tracks usually show slight rustingnot sufficient to affect their performance over many years. The fact that energy is consumed in the reduction process means that the metal has a higher energy state than the metal compound this in turn means that the metal is unstable and tends to revert to the combined form when it comes into contact with non-metals in the environment. i.H2O. The famous iron Delhi Pillar in India was made almost 2000 years ago and is almost as good as new. fluxing of the lining of a steelmaking furnace. rubber. For purposes of this book we include ceramics. plastics. and other nonmetallic materials. rust.
This also applies to power production. sulfur. In general. and lower production costs. Many of the present-day operations would 6 . Higher temperatures and pressures usually involve more severe corrosion conditions." For example. greater speed. than to the oil. Fig. and water.1 Metallurgy of iron 3.4. and rusting of steel by water and oxygen results in a hydrated iron oxide. hydrogen sulfide. and formic: alkalies. naphtha. and nitric: organic acids such as naphthenic. including nuclear power. Some examples are air and moisture: fresh. although many other metals form their oxides when corrosion occurs. and mine waters: rural. better yields. soils: solvents: vegetable and petroleum oils: and a variety of food products. Environments Practically all environments are corrosive to some degree. sulfur dioxide. Most iron ores contain oxides of iron. distilled. acetic. and fuel gases: mineral acids such as hydrochloric. urban. or gasoline. the "inorganic" materials are more corrosive than the "organics. salt. hydrochloric and sulfuric acids. Rusting is a term reserved for steel and iron corrosion. sulfuric. and many other methods and processes.Extractive metallurgy is concerned primarily with the winning of the metal from the ore and refining or alloying the metal for use. ammonia. The trend in the chemical process industries toward higher temperatures and pressures has made possible new processes or improvements in old processes for example. and industrial atmospheres: steam and other gases such as chlorine. corrosion in the petroleum industry is due more to sodium chloride. missiles.
a black sulphide tarnish on silver is aesthetically undesirable and also has a detrimental effect on properties if the silver is used. However. as an electrical contact. In so far as any conversion of a metal to its corrosion products must be regarded as detrimental to the metal it could be said that corrosion is always detrimental. but this depends on the rate of corrosion and its extent in many systems the rate may be so slow that its effect is negligible. although as will be seen this obviously depends on the rate of corrosion and the extent to which it has proceeded. It is important to emphasize that whereas the mechanical and physical properties of metals and alloys are independent of the nature of the environment the converse applies to their corrosion properties. Thus in specifying the tensile strength of a mild steel of given composition it is not necessary to specify the environmental conditions prevailing during the actual determination. the corrosion rate of mild steel obviously depends on the environment and.5. Other definition of corrosion Metals are used for engineering constructions because of their mechanical properties. for example. while in others it may be so high that its consequences are catastrophic.not have been possible or economical without the use of corrosion. since implicit in this term arc a number of different concepts. but for the purpose of this work the following definition will be adopted: reaction of a metal or alloy with its environment with the formation of corrosion products. and although the formation of thin surface films (tarnish films) has little effect on mechanical properties they are detrimental to appearance and to other properties. in others it may be significant but tolerable. Metals are also used because of their aesthetic appeal. which in any case requires only a few minutes in a tensile-testing machine. 3. is far more rapid in an industrial 7 . for example. A precise definition of corrosion is not as simple as might be thought. and clearly these are affected by the conversion of the metal into corrosion products.resistant materials.
NH4C1 and (NH4)2SO4. the major application for coatings is for the protection of structures and components that are in contact with natural aqueous environments. a stainless steel of the type 18Cr-10Ni-3Mo will be virtually uncorroded and its surface remain bright and reflecting. However. i. rural. outdoor and indoor exposure) and waters (fresh. As far as the atmosphere is concerned it should be noted that. brackish. Metal coatings arc used to protect the substrate from corrosion in a variety of environments that range from acid fruit juices to high temperature combustion products. for example. and this too has a significant effect on the corrosion rate. which include various atmospheres (industrial. with the exception of the sulphide tarnishing of silver and copper. seawater. and polluted water). in general. a polluted industrial atmosphere is far more corrosive than a rural atmosphere. should also be noted that the atmospheres in locations near the sea arc contaminated with particles of salt. hard waters 8 . depends upon the precise environmental conditions to which it will be subjected in service. marine. As far as different metals and alloys arc concerned each has a specific corrosion rate in a given environment. Different waters vary significantly in (heir corrosiveness. the corrosion rate. Contaminants in the atmosphere can markedly affect the corrosion rate. for example sea water is more corrosive than fresh natural waters. It follows that the corrosion of a given metal. It. the presence of water on the metal surface is an essential condition for aqueous corrosion and that this may range from a thin condensed film of moisture resulting from fluctuations in temperature to completely wet conditions resulting from heavy rainfall. and each environment presents special problems. whereas mild steel corrodes rapidly when exposed to an industrial atmosphere. How.ever.e. and this applies particularly to gases such as SO2 and H2S and to solid particles –such as carbon.polluted atmosphere than in a clean rural atmosphere it is also more rapid in sea water than in fresh potable water.
and lower production costs. hydrochloric and sulfuric acids. The trend in the chemical process industries toward higher temperatures and pressures has made possible new processes or improvements in old processes for example. Some examples are air and moisture: fresh. can act as a barrier that partially isolates the metal from the environment. ammonia. or gasoline. In general. and mine waters: rural. and formic: alkalies. than to the oil. including nuclear power. distilled. sulfur dioxide. and fuel gases: mineral acids such as hydrochloric. sulfuric.6. soils: solvents: vegetable and petroleum oils: and a variety of food products. 9 . acetic.(fresh or saline) contain calcium bicarbonate and magnesium sulphate in solution. Many of the present-day operations would not have been possible or economical without the use of corrosion. and many other methods and processes. better yields. hydrogen sulfide.resistant materials. the "inorganic" materials are more corrosive than the "organics. This also applies to power production. Similar considerations apply to insoluble corrosion products formed from the metal substrate or metal coating. Environments Practically all environments are corrosive to some degree. and nitric: organic acids such as naphthenic. naphtha." For example. greater speed. 3. salt. if deposited on the surface of a corroding metal or within discontinuities in a coating. corrosion in the petroleum industry is due more to sodium chloride. and the increase in pH produced by the cathodic reaction results in the precipitation of insoluble calcium carbonate and magnesium hydroxide: Decrease in pH CaCO3 + H2CO3 Ca(HCO3)2 MgSO4 + 2 NaOH Mg(OH)2 + Na2SO4 These insoluble compounds. Higher temperatures and pressures usually involve more severe corrosion conditions. sulfur. and industrial atmospheres: steam and other gases such as chlorine. and water. missiles. urban.
but the search is by no means complete. the 10 . At the anode. in which case the voltage is expressed as either “positive” or “negative”. The electrical potential of a metal may be more or less than the standard. many areas remain unexplored or litter understood. the cathode is the region of higher potential. These sites constitute the corrosion cell. This voltage can be measured when a metal is electrically connected to a standard electrode.7. However. In general the lower the potential of the anode. This difference in potential allows current to pass through the metal causing reactions at anodic and cathodic sites. Corrosion Theory The search for a better understanding of the actual mechanism has been actively pursued for over a hundred years. our current knowledge of what takes place during the corrosion process has been sufficient to create effective tools to combat corrosion in most situations. Fig. as in Figure 2 The anode is the region of lower potential. We understand what occurs during many corrosion processes.2 Corrosion cell Conversely. Corrosion is an electrochemical process in which a difference potential develops between two metals or between different parts of a single metal. metal ions go in to solution.3.
seawaters are generally more corrosive than surface supplies. 11 . Thus. Any metal immersed in water will soon develop a measurable potential. temperature and velocity. and that in practical situations. Those of lower potential can be expected to corrode more easily and extensively than those of higher potential. In an actual situation. The extent of the corrosion is also a function of the capability of ions and electrons to travel through the water phase and participate in chemical reactions. if a pair of metals of different potential was coupled.3 Galvanic Series of some commercial metals and alloys in seawater It should be noted that the measured potentials shown in the illustration were developed under specific conditions of composition. Theoretically. the actual conditions may differ. the one of lower potential would become the anode and actively corrode Fig.greater the amount of metal dissolution and the more serious the corrosion problem. we can therefore assume that if two metals are coupled. Waters high in dissolved solids are more conductive and cause more severe corrosion problems.
8. The electrons migrate through the metal to cathode area where they react in any one of several ways. Corrosion Reactions It has been demonstrated that potential differences within a metal. Anodic reactions are typified by the dissolution of iron: Fe → Fe+2 + 2e– Analogous reactions occur in other metals. Some typical cathodic reactions are as follows: a.Oxygen reduction of water O2 + 2H2O + 4e – → 4OH Important in natural.Sulfate ion reduction 12 .. c. e. aerated waters. Many other factors must be considered before predictions can be safely made. f. turbulent conditions (e. d. b.Reduction of water 2H2O + 2e– → H2↑ + 2OH– Occurs normally in natural waters. The result of coupling two metals of closer potential is more difficult to predict.g.Oxygen reduction O2 + 4H + + 4e – → 2H2O Occurs in aerated acidic solutions. acid cleaning). 3.Ferric ion reduction Fe+3 + e– → Fe+2 Occurs under acidic.Hydrogen ion reduction: 2H+ + 2e– → H2↓ Important in acidic solutions. will cause chemical reactions at the anode and cathode.problems within the system would probably exit. or between two metals. these are discussed below.
negatively changed ions. and d. Thus. including corrosion products and inclusions. If a porous can continue. or microbiological slime.4H2 + SO4–2 → S2 + 4H2O Occurs in the presence of sulfate reducing bacteria. g. they may cause the precipitation of other ions from the water. The structure of the entire surface film. adherent film is formed. b. redrust and hydrated ferric oxide: 2Fe(OH)3 → Fe2O3↓ + 3H2O Fe(OH)3 → FeOOH↓ + H2O As solid corrosion products are precipitated at the anode. ionic diffusion is 13 . such as hydroxyl ions produced at the cathodic migrate to the anode of the corrosion cell. Hydroxyl ions will combine with the ferrous cations produced by dissolution of the metal: Fe+2 + 2OH– → Fe (OH) 2↓ The ferrous hydroxide produced has a very low solubility and is quickly precipitated as a white floc at the metal-water interface.Metal ion reduction (Plating) M+S + Ne– → M Involves more noble metals in solution. This movement of ions can cause additional reactions at the anode. The most frequent cathodic reactions are a. sand. c. clay. however. Positively charged ions will move toward the cathode. is a major factor in determining the total amount of corrosion products and in the total amount of corrosion which will take place. a tight. The floc is then rapidly oxidized to ferric hydroxide: 4Fe(OH)2 + O2 + 2H2O → 4Fe(OH)2↓ Dehydrolysis of this product leads to the formation of the corrosion products normally seen on ferrous surfaces. or such suspended matter as mud. a corrosion film may show trades of hardness salts. If. because metal ions can penetrate it and reach the solution interface. silt.
The degree to which such a film can impede corrosion is a complex function of the corrosion reactions.9. 14 . the specific problems encountered in any plant’s operations are.0 in natural. Chemical Factors: A number of factors determine the extent of an aqueous corrosion problem: some are external and some relate to the composition of the metal under consideration. the solution just outside the node is mildly alkaline since it is generally saturated with ferrous hydroxide. in the case of ferrous-based materials. will provide answers to questions involving such factors as differences in potential between two portions of a metal and the degree of associated corrosion.10. Initially. Therefore. However. In time. These aspects are discussed briefly to establish general guidelines. including dissolved and suspended matter. Most corrosion occurs at the beginning of a metal’s service life.3. where there is free mineral acidity in the water. is integral to the subject of corrosion control. the corrosion.3 and 10. similarly unique. Often. below pH 4. the structure of the deposit and the water velocity. metal dissolution is not impeded by a film of corrosion products. including the metal structure itself. or halt. the film will retard. 3. Proper corrosion control requires that each case be considered separately. small changes in pH do not seriously affected the degree to which steel is corroded. pH: Between pH 4.prevented and the metal will no longer dissolve. in a sense. the treatment program that works well for one plant may fail at a neighboring installation. Water Composition: The nature of the water phase. Understanding the ramifications of the metal’s aqueous environment and evaluating certain physical aspects of the total system. The exact constituents of the water phase are unique to any one water supply or application. 3. aerated waters at normal temperatures.
Variations in the macrostructure of the metal or in the water interface become more important. Most metals falls in to the first category. 15 . The actual effect of pH on a particular metal is determined by the behavior of its oxide. these metals are referred to as “ amphoteric”. the metal will corrode rapidly in this environment. The metal will have its greatest stability.5. Occasionally a metal oxide will dissolve in both acid and alkaline solutions. there will be extensive corrosion in the pH range. respectively. at some intermediate pH range. overvoltage plays a more significant role in the corrosion process.corrosion progresses rapidly. In this pH range. will behave in this way.5 and 11. from a corrosion standpoint. those at the top of the galvanic series. If the oxide is readily dissolve in alkaline media. “Noble ” metals. If the oxide is soluble in acidic media. Some metal oxides are insoluble at any pH. Their corrosion rates are minimal at pH 6. Their corrosion rate will therefore be independent of pH. Aluminum and Zinc are amphoteric.
this results from hydrogen evolution. iron behaves amphoterically: The corrosion rate again begins to rise with increasing pH. because oxygen depolarization is the principle factor determining corrosion. Any further pH increase reduces the corrosion rate.3 and 10. A number of odd trends are evident in the behavior of iron. the corrosion rate is less influenced by pH.0.Fig. until a minimum value is attained at about pH 12.4 Variation in corrosion rate with pH value . 16 . iron reacts with strong caustic solutions to liberate hydrogen and form the ferroate ion. At this point.0. Interestingly enough. Fe +2NaOH → Na2FeO2 +H2 Thus we see that hydrogen evolution controls corrosion of ferrous based materials at both extremes of the pH scale. Between pH 4. the behavior is similar to that of an acid-soluble metal. As the pH increases to 4.
In a dilute solution. For a concentrated solution. and to a lesser extent. hardness ions and alkalinity have an inhibiting effect on corrosion. local anodic sites. The ionic constituents in normal waters have various effects on the corrosion rate. and surface area. Three typical examples of these are ammonia. the sulphate ion are capable of penetrating passive films and setting up highly active.11. Dissolved salts The corrosion rate for metals associated with natural. Carbon dioxide The gradual solution of carbon dioxide into water will decrease pH by the formation of carbonic acid. Dissolved oxygen in the water acts as a cathodic 17 . pressure. as a result precipitation of dissolved salts as their solubility products are reached. these include carbon dioxide and oxygen. increased electrical conductivity causes the corrosion rate to increase. Conversely. Dissolved Gases A number of gases are normally found dissolved in water. Other gases may also be present as a result of contamination or other control programs.12. hydrogen sulfide and chlorine. precipitation could quite possibly result in a barrier film which would retard corrosion. at normal temperature.3. The corrosion rate may thereafter decrease in more heavily concentrated solutions. For instance. will accelerate as the concentration of the dissolved salts in the water increases. the precipitated products of various hardness salts often inhibit corrosion. 3. the chloride ion. CO2 + H2O H2CO3 Oxygen The amount of dissolved oxygen in water is directly related to its temperature. low-solid water. which adds acidity to the water and thereby promotes hydrogen evolution.
On many metals it also 18 . The gas promotes active corrosion in two ways. promoting. it causes low pH attack. This action reduces the pH of the recirculating water and causes increased corrosion. Chlorine Chlorine gas is the most commonly used toxicant for the control of micro organisms in cooling water systems. NH3 + H2O NH4OH NH4OH + Cu+2 Cu (NH3)+2 +H2O This soluble copper-ammonium complex is very corrosive to copper. Because it is acidic. This leads to the formation of an active anodic site under the deposit and severe localized corrosion. or biological growth. It normally results from process contamination. A special case of oxygen corrosion is mentioned briefly here and discussed later in this chapter. Any porous deposit on a metal surface. Hydrogen sulfide Hydrogen sulfide is one of the most harmful gases that can enter a cooling water system. a differential aeration cell is set up. or is produced by the reduction of sulfate ions by sulfate-reducing bacteria. corrosion. Upon entering the water. It will selectively corrode copper in the presence of oxidizing agents. it is responsible for the formation of iron sulfide which is cathodic to iron and leads to galvanic corrosion.depolarizer. will almost always have an oxygen-deficient environment underneath it. suspended matter. A very common manifestation of this is under-deposit corrosion. it hydrolyzes to form hypochlorous and hydrochloric acid. whether from precipitated salts. When a water has unequal oxygen concentration. Secondly. Especially in refineries and petrochemical plants. Ammonia Ammonia is generally introduced in to water as a result of process contamination.
The existence of an anode merely indicates that there is a potential for corrosion current it does not determine the rate of corrosion. which can cause more corrosive damage than precipitated salts. clay. similar to the action caused by dissolved oxygen. Produced hydrogen sulfide by reduction of the sulfate ions found in almost all water supplies. An understanding of their roles can help to assure optimum design and improved operating character related to corrosion control in the future. Relative Metal Areas It has already been demonstrated that the coupling of two dissimilar metals will produce a difference in potential between them with the more negative becoming the anode. Microorganisms Microorganisms' growth often presents very special problems. Causing depolarization of the corrosion cell. Suspended matter Mud. In areas of the system where sedimentation of these materials take place. Such sulfate oxidizers as the Thiobacillus oxidize the sulfate ions to sulfuric acid and cause low pH attack. This is governed by other factors such as the relative areas of the cathode and anode. dirt and other particles may enter a cooling water system either as airborne contamination or as part of the system’s makeup water supply. Hydrogen is metabolized by many species. a type of sulfate-reducing bacteria. Physical Factors A system’s design and operating characteristics are often determining factors at the onset and continuance of corrosion. Porous deposits are easily formed and differential aeration cells are quickly established. 19 . Desulfovibrio desufuricans. Anaerobic bacteria form differential aeration cells and accelerate local attack. sand.retards formation of certain protective corrosion inhibitor films. Some species produce acidic compounds.
relative area effects are extremely important. For example. In brackish water or seawater. a rise in temperature from 60F to 176F may increase corrosion as much as 400 percent. In a tube-to-tube sheet joint in a seawater heat exchanger using steel tubes and a nickel tube sheet extensive corrosion of the steel tubes could be expected. thereby depolarizing the corrosion cell. because the solution’s conductivity is low. as temperature rises. in a domestic water system. corrosion rates increases with rise in temperature. Overvoltage decreases causing depolarization by hydrogen evolution. In an open system. In general. The net effect is an increase in the amount of dissolved oxygen reaching the metal surface. Increased diffusion enables more dissolved oxygen to reach a cathodic surface. An increase corrosion in inhibitor levels would consequently be necessary to minimize this problem. Temperature: The extent of corrosion increases with temperature. because diffusion rates have also increased. In dilute solutions. and both overvoltage and viscosity decrease. A decrease in viscosity aids both depolarization mechanisms because it favors solution atmospheric oxygen and enhances hydrogen evolution. deposit the decrease in the solubility and availability of dissolved oxygen. This trend continuous until 20 . The relative-area effects become more important as the conductivity of the solution increase. For example. Reversing the situation results in far less corrosion of steel between the ratio of cathodic to anodic area is small. In the evaluation of a nickel-steel couple. the galvanic series indicates that the nickel is cathodic to steel. The effect of relative areas also applies to a single metal. only the cathodic area immediately around the anode is important.The rate of corrosion increases in proportional to the ratio of cathodic area to anodic area. A small rupture in the oxide film of a passivated metal will cause extensive corrosion because a small anode has been created in a large cathodic field. diffusion increases.
a conditions which explains active corrosion in systems subjected to unequal heat transfer. Heat transfer Heat transfer surfaces such as those in cooling water systems are particularly difficult to protect. Some metals or alloys change their electric potential as temperature rises. Fig.about 170F. These can lead to “hot wall effects” in which oxygen is released from solution at the hot metal surface and promotes the formation of a differential aeration cell.5 Galvanic cell caused by difference in temperature 21 . and a problem often experienced in fouled heat exchangers. The zinc coating on galvanized steel be comes cathodic to the ferrous portion at about 150F and no longer provides corrosion protection. when the dissolved oxygen exceeds the amount made available by diffusion. This is shown in figure (6). as shown in Fig . This is attributed to high skin temperatures along the metal surface. corrosion increases steadily as temperature rises since oxygen under pressure cannot escape. The net effect therefore is an increase in diffusion rates. Any temperature variation within one piece of metal will cause the warmer portions to become anodic to the cooler areas. In a closed system.
g. there is a thin. Figure (?) illustrates this effect graphically using corrosion in a condenser tube as an example. high velocity waters remove what might have become a passivating layer as corrosion product. Dissolved oxygen is distributed rapidly by turbulent mixing through the bulk of the fluid but encounters more difficulty in diffusing through the laminar zone to reach the metal. (a) Low velocity laminar flow (b) High velocity turbulent flow (c) Very high velocity turbulent flow For inhibited water there is a compensating factor. or low velocity areas in a cooling systems e.Velocity There are two categories of water flow laminar and turbulent. so does inhibitor diffusion. shell side water flow heat exchangers are difficult to protect at normal inhibitor levels. Therefore. 22 . In addition. As oxygen diffusion to the metal surface increases. These are shown in Fig . producing the net effect of accelerated corrosion. cooling water systems in a standby condition. the thinner the laminar layer. laminar film of water along the metal surface.6 Velocity distribution in laminar and turbulent flow..Even in turbulent flow. Fig. As velocity (turbulence increases. less corrosion inhibitor is required at higher velocities conversely. Laminar flow is low in velocity and may not be consistent across the metal surface. the depth of the laminar zone decreases and more oxygen can reach the metal surface. however. the greater the turbulence. Turbulent flow is at a rate and distribution nearly that of “plug flow” (maximum velocity turbulent flow).
fretting or cavitation effects. If a galvanic cell is set up by the coupled metals. The extent of corrosion is determined by many of the factors discussed in the previous section. 23 . negating any relative area effects area favorable to corrosion in the system would obviously decrease the potential difference between the metals and neutralize the corrosion reaction. relative areas. solution conductivity and polarization mechanisms being the most important. Inhibitors that are effective in the absence of some or all of these phenomena may not be so in their presence. Fatigue. In the design of equipment where galvanic corrosion may be a problem. In such a cell. If the ratio of cathodic to anodic surfaces is low.Dissimilar metals: Any metal coupled to one above it will become the anode. plastic sleeve or insert. In fact it may not always be possible to use inhibitors successfully in their situations and methods of corrosion prevention will be required. dissimilar metals should be separated by a non-conductive substance such as a dielectric union. the iron becomes the protected cathode and the magnesium the scarified anode. Galvanic corrosion will be limited. Typical examples include the presence of inherent or applied stresses. Galvanic cells may be used to advantage to protect a given metal. In many situations. hydrogen will be reduced on the cathodic metal and absorbed on its surface. Mechanical effects Corrosion can often be initiated or intensified by the conjoint of mechanical factors. solution conductivity and relative areas. iron is protected by coupling it to a less noble metal such as magnesium. Solutions of low conductivity also limit galvanic attack because only the immediately adjacent cathode areas are associated with the anode.
An increase in metal purity provides no guarantee that corrosion will decreased. Combating Corrosion The following items should be considered as means of combating corrosion. the controlling factors are the corrosion reactions themselves. especially if the precipitates more noble than the metal itself. Those areas will become anodic in the rest of the metal. in which the potential for electron loss and metallic ion formation increases. Aluminum and iron may serve as example of constructing behavior. Inclusion of a non-homogenous metal or other metallic compound in the grain structure results in the formation of a small galvanic cell in that area. it is not the most corrosion-resistant material. All have surface flaws such as scratches. Since this is the most important method of preventing or reducing corrosion damage. Select Proper Material The most common method of preventing corrosion is the selection of the proper metal or alloy for a particular corrosive service.Metallurgy: Metals are never absolutely flat.1. Pure iron is the more resistance to corrosion than cast iron or steel. Aluminum’s resistance to corrosion increases as its purity does. In the case of aluminum. and it is not a specific alloy. plane structures. Anodic site formation may result from a number of causes detectable under microscopic inspection. Stainless steel is not stainless.13. corrosion protection depends upon the formation of oxide films. 3. 3. Precipitation at metal grain boundaries will cause a corrosion cell to form. Stainless steel is the generic name for a series of more than 30 24 . For iron. One of the most popular misconceptions to those not familiar with metallurgy or corrosion engineering concerns the uses and characteristics of stainless steel.13. A stressed metal would normally set up anodic sites at certain intergranular boundaries. which is aided by increases in purity. Two adjacent grains of different density might create a corrosion cell. He resistance of iron remains the same as its purity increases.
Stainless alloys are more susceptible to localized corrosion such as intergranular corrosion. but it should be remembered that they do not resist all corrosives. This is based on the belief that nonmagnetic stainless steels represent "good" alloys. This test has no basis and. Many stainless steel alloys are magnetic." Stainless steels represent a class of highly corrosion resistant materials of relatively low cost that should be carefully used. together with other alloy additions.different alloys containing from 11. In fact. Monel-hydrofluoric acid 4. Stainless steels-nitric acid 2. These combinations of metal and corrosive usually represent the maximum amount of corrosion resistance for the least amount of money. In alloy selection. and pitting attack than ordinary structural steels.5 to 30% chromium and 0 to 22% nickel. Nickel and nickel alloys-caustic 3. under certain conditions. Under certain conditions many of the magnetic stainless steels are superior to the nonmagnetic varieties. stress-corrosion cracking. Frequently. Some of these natural combinations are as follows: 1. and stainless steels that are magnetic are inferior. in fact. Stainless steels have widespread application in resisting corrosion. the quality of stainless steels is checked with a magnet. stainless steels are less resistant than ordinary structural steel. In summary. such as chloride-containing mediums and stressed structures. there are several "natural” metal-corrosive combinations. There is no correlation between magnetic susceptibility and corrosion resistance. a large number of corrosion failures can be directly attributed to the indiscriminate selection of stainless steels for construction on the basis that they are the "best. is misleading. Hastelloys (Chlorimets)-hot hydrochloric acid 25 . and many of the cast austenitic stainless steels show some ferromagnetic properties.
26 . as these have excellent resistance to this medium under a wide range of exposure conditions. Tin or tin coatings are almost always chosen as a container or piping material for very pure distilled water. Lead-dilute sulfuric acid 6. but usually accurate. For oxidizing conditions. For reducing or nonoxidizing environments. tantalum has been considered and used as an "ultimate" corrosion-resistant material. For this reason. manufacturers of glass-lined equipment use tantalum plugs to seal defects since this material matches the resistance of glass. Tin-distilled water 8. and their alloys are frequently employed. Tantalum-ultimate resistance 10. nickel. Tantalum is resistant to most acids at all concentrations and temperatures and is generally used under conditions were minimal corrosion is required. titanium and its alloys have shown superior resistance. copper. For extremely powerful oxidizing conditions. such as implants in the human body. the stainless steels are usually considered first. Aluminum-nonstaining atmospheric exposure 7. In many instances. rules that may be applied to the resistance of metals and alloys. An interesting feature about tantalum is that it almost exactly parallels the corrosion resistance of glass. such as air-free acids and aqueous solutions. Titanium-hot strong oxidizing solutions 9. chromium-containing alloys are used. For many years.5. Steel-concentrated sulfuric acid The above list does not represent the only material-corrosive combinations. Both glass and tantalum are resistant to virtually all mediums except hydrofluoric acid and caustic solutions. For nitric acid service. cheaper materials or more resistant materials are available. There are some general.
3. Alter Environment Simple changes in environment may make an appreciable difference corrosion of metals and should be considered as a means of combating corrosion . the use of dissimilar metals contact with each other should generally be avoided particularly if they are widely separated in their nominal positions in the electromotive series if they are to be used together . include the desirability. with respect to minimizing corrosion difficulties should.13. Proper Design Design considerations.3. Butt joins should be used wherever possible.3. the treatment of boiler feed water for instance to remove oxygen greatly reduces the corrosiveness of the water on steel . inspection during fabrication and prior to acceptance is desirable . porous insulation should be weatherproofed or otherwise protected from moisture and spills to avoid content of the wet material with the equipment . Inert gas purging and blanking of many solution particularly acidic media generally minimizes corrosion of copper and nickel base alloys by minimizing air or 27 . equipment should be supported in such a way that it will net rest in pools of liquid or on damp insulating material . specifications should be sufficiently complete ensure that the desired composition or type of material will be used and the right condition of heat treatment and surface finish will be provided .13.2. consideration should be given to insulating then from each ether making anodic material area as large as possible . If lap joints employing fillet welds are used the welds should be continuous on the process side. for free and complete drainage elimination of crevices and case of cleaning and inspection the installation of befits stiffeners and drain nozzles and the location of valves and pumps should be made so that free drainage will occur and washing can be accomplished without hold up means of access for inspection and maintenance should be provided wherever practical. Oxygen is an important factor and its removal or addition may cause marked changes in corrosion.
oxygen content corrosiveness of acid media to stainless alloyed on the other hand may be reduced by a reaction because of the formation of passive oxide films . Where pH values can be modified it will generally be beneficial to hold acid level to a minimum where acid additions are made in batch processes . Reduction in temperature will almost always be beneficial with respect to reducing corrosion. Various forms of corrosion are schematically in figure (7) and listed as follows: (The order of listing is somewhat arbitrary) Uniform corrosion Galvanic corrosion Crevice corrosion Pitting corrosion Environmental induced cracking Hydrogen damage Intergranular corrosion Deallyoing Erosion corrosion 28 . Elimination of moisture can and frequently does minimize . it may be beneficial to add then last so as to obtain maximum dilution and minimum acid concentration and exposure time . Alkaline pH values are less critical than acid values with respect to controlling corrosion . if not prevent corrosion of metals and this possibility of environment alteration should always be considered . Reduction in velocity and turbulence will generally result in reduced corrosion an exception being where solids may collect on surface and case pitting.
magnetite or 29 . The second material may be part of a fastener (bolt. sand. the more noble alloy Uniform corrosion accounts for the greatest tonnage of metal consumed. 3. At the same time. noble potential in the Galvanic Series. Crevice corrosion seems to be the preferred title for metal-metal crevices. Galvanic Corrosion When two dissimilar alloys are coupled in the presence of corrosion electrolyte one of them is preferentially corroded while the other is protected from corrosion. The various useful alloys are listed in order of Ecorr in the abbreviated Galvanic Series that appears in Table (1).. The negative.14. Deposit corrosion and gasket corrosion are terms sometimes used when a nonmetallic material forms a crevice on the metal surface. rivet.Fig. a deposit of mud.7 Schematic summary of the various forms of corrosion. If the crevice is made up of differing alloys or if the deposit is conductive (e. Any alloy will be preferentially corroded when coupled to another alloy with a more positive or is protected from corrosion. or other insoluble solid. or a nonmetallic gasket or packing. Crevice Corrosion Corrosion of an alloy is often greater in the small sheltered volume of the crevice created by contact with another material.g. and washer) of the same or a different alloy. preferentially corroded alloy in the couple is said to be active in the Galvanic Series.
Fig. while the outer surfaces can drain and dry.graphite). the bolt in figure was heavily corroded within the crevice as compared to the outer surfaces. Thus.8 Galvanic corrosion of a carbon steel pipe flange welded to stainless steel pipe Corrosion within a crevice may be caused in atmospheric exposures by retention of water. crevice corrosion may be compounded by galvanic effects.9 Corrosion of steel bolt in an industrial environment resulting from continually wetted area within a crevice 30 . Fig.
15. The pit is a self-serving crevice that restricts transport between the bulk solution and the acid chloride pit anode. the main components of stainless steel. Corrosion products of Fe. Cr. Pitting corrosion Localized attack in an otherwise resistant surface produces pitting corrosion. An example of crevice corrosion of stainless steel in hot salt solution is shown in figure The anode is isolated in the crevice with the surrounded passive surfaces acting as the cathode. The pits may be deep. accumulated in the crevice and form very acid chloride solutions in which corrosion rates are very high.Crevice corrosion of stainless steels in aerated salt solutions is widely known. The stainless steels and nickel alloys with chromium depend on a passive film for corrosion resistance and are especially susceptible to pitting by local breakbown of the film at isolated sites. Standard exposure and 31 . and Ni. shallow.10 crevice corrosion of drilled and tapped stainless steel test specimen in 3% NaCl solution at 90C 3. Fig. as shown in figure (8). or undercut. Pitting shares the same mechanism with crevice corrosion in stainless steels.
A specific dissolved species is often required.11 Stress corrosion cracking at a U-bend . Figure shows an example of stress corrosion cracking in a U-bend test specimen. Brass in ammonia solutions. corrosion fatigue cracking (CFC). and hydrogen stress cracking. and corrosion rates are consequently quite low. and carbon steel in nitrates. Three related but distinct types of failure are included in EIC: stress corrosion cracking (SCC). stainless steels are susceptible in hot chlorides. Alternative terms for HIC are hydrogen embrittlement. Hydrogen-assisted cracking. as well as the electrochemical theory behind crevice and pitting corrosion. Fig. 3. Stress corrosion cracking occurs in alloys with a static tensile stress in the presence of specific environmental conditions. Further discussion of critical environments for most of the important constructional alloys are summarized in different tables. Pure metals are comparatively resistant to stress corrosion cracking. Environmentally induced Cracking Brittle fracture of a normally ductile alloy in the presence of an environment that causes minimal uniform corrosion is defined as environmentally induced cracking (EIC). A passive surface film under oxidizing conditions must be present.16. 32 . And hydrogen-induced cracking (HIC).electrochemical testing methods are described. For example.
Corrosion fatigue cracking occurs under cyclic stresses in a corrosive environment. electroplating. A good example of beach marks is shown in Figure . Hydrogen induced cracking is caused by hydrogen diffusing into the alloy lattice when the hydrogen evolution reaction. cracks have a very similar appearance otherwise. H2 produces atomic hydrogen at the surface during corrosion. and beach marks may be present with little or no visible corrosion. cleaning and pickling. However. whereas stresses corrosion cracking and corrosion fatigue cracking are suppressed. or cathodic protection. 2H+ + 2e. However. Hydrogen induced cracking usually predominates over stress corrosion 33 . Susceptibility to and rate of fatigue cracking without corrosion are usually increased in the presence of a corrosive environment. Fig. hydrogen induced cracking is accelerated by cathodic polarization. Although stress corrosion cracks often show more branching.12 Beach marks on the fracture surface of a fatigue failure . and no specific environment is required. Macroscopic beach marks are often observed where tarnish or corrosion products accumulate during discontinuous propagation of the crack front. beach marks may also be caused by differences in microplastic deformation when crack propagation is interrupted. Both alloys and pure metals are susceptible.
and surface blisters. which have been studied extensively by aircraft and aerospace manufacturer. Hydrogen Damage Hydrogen induced cracking (HIC) and the impairment of ductility by relatively low levels of hydrogen are reversible to some extent if the hydrogen is permitted to escape by baking at elevated temperature. Hydrogen blisters or smaller hydrogen cracks become evident when internal hydrogen-filled voids erupt at the surface. where molecular hydrogen gas can nucleate. aluminum alloys.cracking in carbon and low alloy steels. 34 . and thorium. zirconium. Other effects at higher hydrogen levels are usually irreversible. uranium. stainless steels. magnesium. vanadium. Voids. resulting in decarburization. Hydrogen induced cracking also contributes to losses of fatigue life in such strength alloys. generating sufficient internal pressure to deform and rupture the metal locally. and titanium which have been alloyed. tantalum. The other hydrogen damage mechanisms described are also possible in these metals. Hydride formation embrittles reactive metals such as titanium. heat treated. niobium. Voids are formed when atomic hydrogen migrates from the surface to internal defects and inclusions. or cold worked to near maximum strength. Hydrogen attack is the reaction of hydrogen with carbides in steel to form methane.
is a common problem in many alloy systems. or passivating elements such as chromium may be depleted at the grain boundaries.Fig. chromium carbides (mainly Cr23C6) precipitate at the grain boundaries. sometimes called intergranular attack. intergranular corrosion (IGC). The best known form of IGC occurs in austenitic stainless steels when heal treatments deplete the grain boundaries of chromium by metallurgical reaction with carbon.13 Hydrogen blister in AISI 1020 carbon steel Intergranular Corrosion Reactive impurities may segregate. In the temperature range 425 to 815C (800 to 1500F). the grain boundary or adjacent regions are often less corrosion resistant and preferential corrosion at the grain boundary may be severe enough to drop grains out of the surface. As a result. Thus. 35 . The resultant structure is susceptible or “sensitized” to IGC. depleting the grain boundary and nearby structure of chromium.
Dezincification often occurs under deposits and in other nonvisible locations. Uniform or layer dezincification is easily recognizable by the red. and selective leaching of other more 36 . The deformed bolt. Selective leaching and parting area alternative terms used occasionally for the same phenomenon.14 intergranular corrosion of a sensitized stainless steel surface viewed by scanning electron microscopy. The deal loving of brass. In plug dezincification the attack is localized and results in penetration and weakening of brass pipe and tubing. copper-colored material visible on the bolt surface in Figure . Dealloying and Dezincification An alloying element that is active (negative electrochemically) to the major solvent element is likely to be preferentially corroded by dealloying. known as dezincification.Below about 10% Cr. previously ex posed to acidic cooling tower waters. Fig. is a common and frequently cited example. Figure shows an example of intergranular corrosion of sensitized austenitic stainless steel. Zinc is strongly active to copper (Table 1) and readily leaches out of brass. these areas lose resistance and are corroded referentially. leaving behind relatively pure porous copper with poor mechanical properties. and failures may be sudden and unpredictable. shows a weak. brittle layer of uniform thickness. Copper is the most noble of the major constructional metals.
known as graphitic corrosion. Fig. When the old graphitized pipe is disturbed.active alloying elements. leaving behind a weak. escaping hazardous chemicals can contaminate the surrounding soil or cause fatal explosions and fires. porous network of inert graphite that can be scratched with a pen knife as shown in figure (16). silicon. such as nickel. The other major example of dealloying. Graphitic corrosion has occurred primarily in buried cast iron pipe and becomes evident only after decades of service. is the elective leaching of iron from gray cast iron. 37 . and aluminum has also been reported.15 Brass bolt (30% Zn) which was bent to shoe uniform penetration of a dezincified layer.
but the chemical component of the mechanism is evident by the dependence on composition of the flowing corrosive solution. exposes the reactive alloy beneath.16 Graphitic corrosion in a gray cast iron water pipe. Figure shows characteristics horseshoe-shaped pits whose ends follow the downstream flow pattern in copper and brass condenser tubes. 38 . The same stagnant or slow-flowing fluid will cause a low or modest corrosion rate. The attack generally follows the directions of localized flow and turbulence around surface irregularities. Harder alloys (brass and bronze) are more resistant.Fig. Erosion-Corrosion and Fretting Recombination of a corrosive fluid and high flow velocity result in erosioncorrosion. Sand or suspended slurries enhance erosion and accelerate erosion-corrosion attack. Low-strength alloys that depend on a surface corrosion product layer for corrosion resistance arc most susceptible. Alloying elements such as aluminum and nickel. and accelerates corrosion. also improve resistance. more adherent surface films. but rapid movement of the corrosive fluid physically erodes and removes the protective cohesion product film. Erosioncorrosion is a common problem in steel pipe with flowing steam carrying condensate water droplets. which form tighter.
The implosions produce extreme pressure bursts that disrupt surface films and even dislodge particles from the metal itself. which acts as an additional abrasive between the contacting surfaces. and in tube and pipe where large pressure changes are present.17 Brass condenser tube showing erosion corrosion in salt water. Cavitation occurs on turbine blades. often from vibration. again exposing the reactive metal to increased oxide formation. which may eventually result in penetration.Fig. A fine red rouge of iron oxide particles is produced on steel. The motion abrades surface oxide film off the metal surface. the chemical and electrochemical contributions are apparent in benefits from selection of corrosion-resistant alloys and control of solution composition. ship propellers. which then implode (collapse) on the surface. It occurs where velocity is so high that pressure reductions in the flow are sufficient to nucleate water vapor bubbles. pump impellers. The attack takes the form of roughened pits. as in Figure (20). Although largely mechanical. but in the vapor phase. Cavitation is a special case of erosion-corrosion. The erosion is provided by repeated by repeated small movement. between the corroding metal and another contacting solid under load. 39 . The effect is compounded by the oxide debris. Fretting is another type of erosion-corrosion.
Nature of Corrosion Can Corrosion Happen? Why do some metals corrode in certain environments while others do not? The laws of thermodynamics tell us that for a reaction to proceed. 3. and E is the cell potential. the cell potential E must be positive. F is the Faraday constant. 40 .Fig. For electro-chemical react ions: G = -ZFE (5) where n is the number of electrons involved in the reaction. For the reaction to be feasible (G is negative).18 Cavitatior of the cast iron suction bell from a low water pump.17. it must have a negative free-energy change (G).
This potential can be measured with a voltmeter by connecting it to an inert reference electrode placed in the solution. If metal ions are present in the amount of 1 gram atom (i.229 +0. Similarly. we must consider the separate anode and cathode reactions.401 +0.771 +0. E [Fe/ Fe++]. If a solid piece of iron is placed in a solution containing iron ions.714 Volts versus normal hydrogen electrode at 25 C. exists between the iron atoms in the solid and the iron ions in solution. Fe+ O2 + 2H2O + 4e- 4OHCu Cu++ + 2e2H+ + 2e.662 -2. 2H2O Ag Ag+ + eFe+++ + e.440 -0. a half-cell potential exists for the cathode reaction.250 -0.000 -0. a potential difference.744 -0. What is the cell potential? First. unit activity).498 +1. the half-cell potential is called “standard Half-Cell potential”.799 +0. A measured half-cell potential depends on the concentration of the ions in solution.e.e. H2 Ni Ni++ + 2eFe Fe++ + 2eCr Cr+++ +3eZn Zn++ + 2eAl Al+++ + 3eNa Na+ + e+1.337 +0.Table 1 Standard Oxidation-Reduction Potentials Au Au+++ + 3eO2 + 4H+ + 4e. If the latter is known then the half-cell potential at any concentration can be calcu41 . the anode) of a corrosion cell..763 -1. This potential is called a “half-cell potential” because it is for an electrode that can form half (i.
440) = +0. This is actually the rusting of iron in moist air.498 v. All other half-cell potentials are measured relative to that of hydrogen.440 v (1) Since E is positive. 2H+ + 2e. is defined as the potential difference between the cathode and anode half-cells. (5) will be negative. (1). Fe+++ + e. G in Eq.401 – (-0. what will happen? Could it corrode and give hydrogen? The cell potential for this reaction would be: E = 0 . The reaction is impossible because G in Eq. Likewise. If we consider gold in hydrochloric acid. while Fe++ Fe+++ + e. (1) would be positive. Eq. For example.1. is assigned a standard half-cell potential of zero volts. The electrode potential for each of these reactions is numerically the same. (5) is negative.lated from the Nernst equation. For the example of iron in acid solutions: E = E [H+/H2] – E[Fe/Fe++] E = 0 – (-0.is oxidation. for iron in neutral water: E = E [O2/OH-] – E[Fe/Fe++] E = +0. This conclusion is true for all metal/ metal-ion combinations with redox potentials that arc more positive than hydrogen's. the hydrogen reaction.498 =-1. These potentials are also called oxidation-reduction potentials (redox potentials) because they represent oxidation or reduction reactions depending upon the direction. By convention.H2.440) = +0. Fe++ is a reduction reaction. 42 . and the reaction is feasible.841 v) The reaction is feasible because G in Eq. The cell potential E that is used in the free-energy change equation.
and we would have instant and total corrosion.How fast will corrosion happen? To determine the thermodynamic feasibility of a certain corrosion reaction. At the other extreme.e. In practice. we have considered the behavior of independently operating anodes and cathodes with no current passing between them.19 Polarization for iron in acid solution 43 . Ec’ and Ea’ are the cathode and anode potentials. any surface Fig. the resistance approaches zero.. When current flows between the anode and cathode. What about the real case where they are together and short-circuited on a corroding metal? If the electrical resistance in the solution between the anode and cathode were infinite. I = E/R). the current would be infinite. This change is called polarization.. and no corrosion would occur.e. driving force for the reaction decreases) as shown in Fig. if the resistance were zero. Polarization reduces the potential difference between anode and cathode areas (i. The current flowing between the anode and cathode at any point is given by: i' = (Ec’ – Ea’)/R films). at their half-cell level). (6) Where R is the total resistance of the circuit (metal. the current would be zero (Ohms law. then the potentials of the anode and cathode would remain the same (i. solution. respectively. In this condition. which results in a maximum Unite current. the potentials of both change.
18. Once a metal has come to equilibrium in its corrodent. The corrosion potential should not be confused with the previously discussed thermodynamic quantity. for a finite maximum current. g.13 Ie/ Where Rmpy is corrosion rate. R is small. Polarization It is very important to understand the significance of polarization. 3) is a good estimate of the conditions existing during corrosion.. in order to maintain the small potential difference between anode and cathode areas. Methods of measuring the current density will be described in the next article. the rate of corrosion decreases.Because the anodes and cathodes are usually very closely spaced. or greater 44 . I is current density. Ec’ – Ea’ must be small. will be used throughout this series. which drives the current through the circuit. g. 4a. We arc measuring the potential difference between a corroding metal and its ions in solution. e is equivalent weight (chemical) of the metal. Corrosion current density can be converted to a corrosion rate by using Faraday's laws. Therefore. it will have a corrosion potential Ecorr. this change may be small or large as shown in Fig. and is density of metal.. and the point of intersection of the curves (Fig. and a corrosion current density between anode and cathode areas of icorr. and is corroding freely. microamp. As the degree of polarization increases. cm. 3.cm. 3./cu. We have defined polarization as a change in the potential of an electrode as current flows to or from it.. Polarization diagrams of the type shown in Fig. Corrosion potential (Ecorr) can be easily measured experimentally with the setup shown in Fig. cell potential./sq. The polarization on the anode may be less than. Actually. mils/yr. For a given current flow. the true conditions are slightly to the left of the point of intersection. Rmpy = 0.
that on the cathode as seen in Fig.) Fig. The situation is shown in Fig. In this conation. is present in a suitable form and at a 45 . or mineral. Ag. In fact. with the exception of the noble metals Cu. we shall use the mixed polarization case shown in Fig. Metals. The molecule of hydrogen is no longer needed by the corrosion reaction. the cathode operation. 4b and 4c. or polarize. we shall consider a specific example.20 effect of polarization on electrodes Before describing the different types of polarization. carbonates. it is in the way it stays in the cathode area. For simplicity. are the stable form of the metal. Hg and the Pt metals. Au. (The actual curves are not necessarily straight lines as shown in the sketches. hydrogen ions are reduced at the cathode to form hydrogen gas. Hydrogen gas can therefore retard. rather than the metal. etc. When iron corrodes in hydrochloric acid.than. sulphides. To obtain the metal the ore (in which the compound of the metal. are usually found in nature combined with non-metals as oxides. and since these have existed in the earth from time immemorial it follows that these compounds. 4a in most of our examples. corrosion will continue but more slowly than it could if the molecules of hydrogen gas were rapidly moved away.. because it prevents other hydrogen ions from reaching the metal surface and reacting. silicates. 5.
with a consequent increase in energy. in which energy is supplied to the system in the form of chemical. Zn Anodic oxidation: H2O 2 H+ + ½O2 + 2 eIt should be noted that a similar process is used for electroplating zinc. the oxide can be leached from the ore by means of sulphuric acid. and the acid solution of zinc sulphate can then be electrolysed (supply of electrical energy) to give a deposit of zinc metal at the cathode: ZnSO4 + H2O Zn + H2SO4 + ½O2 (Overall reaction). and the subsequent spontaneous conversion of the metal back to a compound 46 . but whereas in the extraction process an inert anode is used (frequently lead) a zinc anode is used in electroplating in order to ensure that the concentration of zinc ions is maintained fairly constant.sufficient concentration for its conversion to the metal to be technologically and economically feasible) is subjected to a reduction process. the zinc metal being oxidized to zinc ions. and the process can be represented by the chemical reactions: 2 ZnO + C 2 Zn + CO2 2 Fe2O3 + 3 C 4 Fe + 3 CO2 Alternatively. which has a greater affinity for oxygen than the metal. This sequence of events in which the mineral is reduced to the metal. in the case of zinc. The overall reaction can also be written in the form of two half-reactions showing the cathodic reduction of zinc ions to zinc metal and the anodic oxidation of water to oxygen and acid (hydrogen ions): Cathodic reduction: Zn2+ + 2e. The fact that energy is consumed in the reduction process means that the metal has a higher energy state than the metal compound this in turn means that the metal is unstable and tends to revert to the combined form when it comes into contact with non-metals in the environment. the anodic reaction in this case is the reverse of equation of cathodic reduction. electrical or thermal energy. For example. the oxides of zinc and iron can be reduced to the metal by using the chemical energy of carbon.
Fig. Indeed if metal extraction is regarded as the winning of a metal from its ores for a profit then corrosion is the converse process. it tends to revert to its oxide Fe2O3.(referred to as a corrosion product. and the subsequent spontaneous conversion of the metal back to the oxide (corrosion product) Thus when iron is exposed to an aqueous environment containing dissolved oxygen. 47 . loss of metal and loss of profit.21 Diagrammatic representation of the energy changes that take place during the chemical reduction of a mineral (hematite. which corresponds in composition to the naturally occurring mineral lepidocrocite.H2O) to the metal 3 (iron). which will occur when it is exposed to the atmosphere or immersed in a natural water.e.H2O. Fe2O3 . rust. which frequently has the same composition and crystal structure as the mineral) with a decrease in energy is illustrated in figure . i.
such as hydrogen chloride or sulfuric. 2 H+ + 2e. Zn + 2 HCL ZnCl2 + H2 Zn + H2SO4ZnSO4 + H2 This equation complete chemical reaction and are balanced. 48 . Each of atoms in the metal surface is in fact an ion occupying its own energy well and stabilized on its position by the electron gas in the metal. If sufficient energy is available about (600 kJ/mol) it will be possible to pull on ion out of it’s energy well in the surface. One ways of generating hydrogen in a laboratory is to place zinc into a dilute acid. open vessel) and 1. the anodic reaction always is the oxidation of metal to a higher valance state. Fe + 2 HCl FeCl2 + H2 Action of Hydrochloric Acid: The hydrochloric acid have bad effect on the metals because chloride ions are strongly absorbed by metals specially steel for example Fe + 2 HCl FeCl2 + H2 During corrosive attack. This gas helps to coment the position ions together and gives the metal its special properties. so forming a highly unstable gaseous metal ions M+Zc which exert a restoring force on the ion.3.19.H2 The corrosion rate of electrolytic iron or low metal iron in IN hydrochloride acid is about 0.2 M Py (150 an agitated acid. Corrosion in Acids Metal Dissolution: Considered the surface of the metal M contained in a vacuum.5 to 2.5 MPy in concentrated acid. The above reaction involves the reduction of hydrogen ions to hydrogen gas according to the reaction.
Hydrochloric acid is the most difficult of the common acids to handle from the standpoints of corrosion and materials of construction. even in relatively dilute concentrations. Metals and alloys are placed in three classifications: 49 . When aeration or oxidizing agents are also present. Materials that show very low rates of corrosion are often not economically feasible. hot strong acid containing substantial amounts of ferric chloride (or cupric chloride) presents a gap that cannot be filled with commercial metals and alloys and many nonmetallics. More and more so-called by-product acid is appearing on the market and being used in the process industries.The corrosion rate in another than dilute solutions increases with hydrochloride acid concentration. Good judgment is required to obtain a good balance between service life and cost of equipment. In fact. The limits for so-called acceptable corrosion rates are usually raised when considering materials of construction for handling hydrochloric acid. These by-product acids could contain any number of impurities. depending on the present process. Almost invariably some iron is present. expensive materials such as tantalum are the only ones that can be utilized. Hydrochloric acid similar sulphuric acid in corrosion properties because it non oxidizing acid. Extreme care is required in the selection of materials to handle the aid by it self. The commercial or muriatic acid often behaves very differently from the chemically pure or reagent grade hydrochloric acid as far as corrosion is concerned. Where contamination is a problem. corrosive conditions may be very rugged. Many unexpected failures in service are explained by the presence of ostensibly minor impurities. and ferric chloride is often a destructive pitting agent. This acid will actively attack many metals with direct replacement of hydrogen gas where this happens the rate of corrosion is rapid. This acid is very corrosive to most of the common metals and alloys. or in process solutions containing appreciable amounts of hydrochloric acid.
even in very dilute solutions. A perhaps more realistic annual $30 billion has been suggested for the sarings that could result if all economically useful measures were taken to prevent or minimize corrosion. Metals and Alloys Ordinary carbon steels and cast iron are never used for hydrochloric acid service. Tin and tin plate are used for solutions containing small amounts of acid such as food products. Aeration or oxidizing conditions result in destructive attack. Plant Downtime Parts and labor to replace corroded equipment are often minor compared to the loss of production while the plant is inoperable during repair. Nevertheless the economic costs of corrosion are obviously enormous. Costs of Corrosion The economic costs of corrosion in the United States of America alone have been estimated between $8 billion and $126 billion per year. 3.(1) Generally used and suitable for most applications (2) Used with caution and under specific conditions (3) Generally unsuitable under any conditions and recommended only for trace amounts of acid.20. 3. These figures are somewhat misleading because zero corrosion assumed as the base line is unattainable. Zinc and magnesium are rapidly attacked by this acid. particularly if appreciable solution velocities are involved. Inhibitors are required when iron and steel equipment is cleaned by pickling with hydrochloric acid. Some measures while reducing corrosion will cost more than the parts or equipment protected. Aeration is also destructive to tin. Rapid corrosion occurs at pH 4 or 5 or below. 50 .21. The most comprehensive study on the economic cost of corrosion in the United States preformed in 1976 estimated an annual cost of $70 billion while the department of commerce has stated the corrosion would cost the United States an estimated $126 billion in 1982.
51 .Loss of Product Leaking container. Human life and safety Corrosion takes an even more significant toll in human life and safety. These are only a few examples of the many such fatal accidents caused by corrosion. These leaks and spills have a corresponding hazardous effect Loss of efficiency Accumulated corrosion products on heat exchanger tubing and pipelines decrease the efficiency of heat transfer and reduce the pumping capacity respectively. tank and pipeline result in significant loss in product. The well-known bridge collapse at pt pleasant west Virginia killed 46 in 1967 and has been attributed to stress corrosion cracking. but a few examples can be cited readily. Some industries Notable the fine chemical and parts of the food processing industry cannot tolerate the pick-up even small quantities of metal ions in their products. Corrosion is never correctly reported as the cause of many fatal accidents. The airline accident in Hawaii has already been mentioned. Over design In Principle of overdesign is the use of much thicker sections than would normally be required for mechanical strength to allow for the ravages of corrosion. which have a high cost.
3. Corrosion products rich in aluminum and oxygen were found to progressively accumulate around the particles and iron was dissolved from the intermetallic. the concentrationof dissolved oxygen (DO) in pipeline. Literature survey HuangY.. followed by back deposition.22. After 32 h of exposure 52 . flow rate and temperature of the electrolyte. it is affirmed that amore reasonable evaluation of internal-pipeline corrosion can be proposed in the monitoring system. backpropagation artificial neural network (BPANN)is employed to estimate the concentration of (DO) of the electrolyte according to the measured factorssuch as the electric current of the galvanic sensor. Based on the comparison between corrosion coupons test and monitoring system. a Cu–Zn galvanic sensor is developed for the internal-pipeline corrosion on-line monitoringsystem..flow rate and temperature of the internal electrolyte. among theelectric current of the galvanic sensor. Copper and manganese did not show any major activity. A complex and non-linear relationship. The results confirmed the cathodic nature of the intermetallics with respectto the aluminum matrix. and the influence caused by theoxidative film on the electrode working face is eliminated by an amendatory correlation coefficient relatingto the electrolyte flow rate and the temperature. SAM and EDX. in which the internalpipeline corrosion state is grasped based on monitoring the corrosion capability of the internal electrolyte environment. Second phase particleswere characterized by AES. After long-term testand analysis. Finally. is acquired. Dawei Jstudied. Grilli R.This work is focused on the role of intermetallics in pitting corrosion of Al2219 alloy. Their behavior in a solution of NaCl was investigated asa function of exposure time. et al . The galvanic corrosion behaviors of the sensor in a simulatedseawater environment are investigated using a 50-m-long pipeline in the laboratory. theeffective working period of the sensor is confirmed.
The developed analytical approach is then applied to some practical galvanic corrosion cases. JeffreyR.. L.. the apparent coalescence of small pits into larger localized corrosion and eventually the appearance of stepped or benched. theoretical expressions for galvanic potentials and currents of one-dimensional systems are deduced and some critical parameters involved in the potential and current equations are systematically discussed. This sequence is typical of that which has been observed many timesand this suggests it is reasonable to infer a generic sequence that describes the changing surface of corroding mild steel in seawater. Anodic regions and micro-pits develop very quickly after first exposure and eventually there is the development of shallow broad pits. This transition of the surfacetopography and the processes involved are still not completely understood. such as a steel–Al joint exposed to bio-fuel E85. 53 . studied the corrosion of mild steel exposed to marine immersion conditions typically is not uniformalthough it is often idealized as such.the largerintermetallics were completely covered. a galvanic couple separated by a passive spacer and a scratched organic coating. perhaps irregularshapedbroad or macro-pits. It is demonstrated that the analytical approach can examine the reliability of a computer modeled galvanic corrosion process and help understand the mechanism behind the computer modeled galvanic corrosion behavior. Melchers R. development of small pits and shallow broad pits. The present paper presentsa number of images typical of the sequential evolution of the surface topology of mild steelcorroding in subtropical coastal seawater. Many practical galvanic corrosion problems can be simplified into a one-dimensional mathematical equation. Song G. The sequence consists of the development of anodicareas. E. It will assist in developing a better understanding of the evolutionof corrosion processes for mild steel in seawater and assist in identifying the various controllingprocesses. In this study.
5 wt.5Cr–1. % Fe alloy. corrosion resistance. and the micro structural changes undergoneby the different alloys employed.5 wt. ionic solutions. 54 . % Fe and Al–1. which can be employed at the sugar industry. such as 0. were prepared in order to study theirhardness.Zumelzu E.84Ni which has high chromium content. with variations in the carbon and nickel content. The behavior of alloys to wear and corrosion depends mainly on the chemical composition and effect of the alloying elements. It is shown that for an Al–0. potentiodynamicpolarization curves and an equivalent circuit analysis were used to evaluate the electrochemical parameters in a 0. coarse cells tend to improve the corrosion resistance mainly due to the reduction in cellular boundaries and for an Al–1. an opposite trend has been detected. Micro structuralcharacterization of alloys was made by scanning electron microscopy (SEM) and electrochemical trials in order to assess corrosion susceptibility were performed with a specific sugar solution. Al–0. wear. aim to evaluate the general electrochemical corrosion resistance of Al–Fe alloys in the range of hypoeutectic compositions.5 M NaCl solution at 25 °C. OsórioW.. EIS plots. and the presence of impurities and inclusionsat a surface level. and wear behavior by means of simulating the conditions found at the sugar industry processes. et al. resilience. the formation of carbides during solidification. R.97C–29. The results obtained in this study made possible the selection of better alloys. High-chromium (14–30%) cast iron alloy samples. Chemical analyses were carried out using atomic absorption to evaluate the deterioration with regard to the attack to chemical composition of alloys.5 wt. % Fe alloy.5 wt. % Fe alloy.
4. Experimental Part
(1) Tank (3) Copper tube (5) Recycle valve (7) Mechanical stirrer
(2) Pump (4) Tank (6) Feed valve
4.2. Materials used
1) 2) 3) 4) K2Cr2O7 (99 %). H2SO4 (98%). 1,5 diphenylcarbazide Acetone
4.3. Run calculations
1) 0.003 M K2Cr2O7: 0.003 M = 0.003 * m. wt. gm/l = 0.003 * 294.18 gm/l ~ 0.883 gm/l Grams in 8 l 0.883 * 8 = 7.064 gm/l of 100% K2Cr2O7 7.064 / 0.99 ~ 7.14 gm/l of 99% K2Cr2O7 2) 1 M of 98% concentration H2SO4: 1 M = 1 * m. wt. gm/l = 1 * 98 gm/l = 98 gm/l Grams in 8 l 98 * 8 = 784 gm/l of 100% H2SO4 784 / .98 = 800 gm/l of 98% H2SO4 ml needed for 8 l ρ = 1.833 gm/ml 800/1.833 ~ 436 ml 3) The rest of 8 l is distilled water
1) 2) 3) 4) 5) 6) 7) 8) Weigh 7.14 gm of K2Cr2O7. Measure 436 ml of H2SO4. Put 6 l of distilled water in the tank. Put the 7.14 gm of K2Cr2O7 in the tank and stir. Put the 436 ml slowly in the tank while stirring. Complete the tank with distilled water till the 8 l mark. Regulate the flow rate by adjusting the 2 valves. Operate the pump and start the run and take sample each constant interval of time starting from t = 0 min till we reach 9 samples.
4.5. Calibration curve
1) Measure 0.5 ml of 0.003 M solution and add 49.5 ml distilled water.
4. 3.5 ml of 3 M H2SO4.4 ml of H 2SO4.2) Measure 7. 4. 3) Measure 4 ml of the solution then add 4 ml of 3 M H2SO4. 4) Measure the absorbance by the spectrophotometer at wavelength 540 nm. 5) Measure 1 ml of the solution then add 7 ml of 3 M H2SO4.6 ml of distilled water.5 ml of the solution then add 0. 8) Measure the absorbance by spectrophotometer for each one at wavelength 540 nm.5 ml of the dye.0003 0.0015 0. 4) Measure 2 ml of the solution then add 6 ml of 3 M H2SO4.075 0.5 ml of distilled water.5 ml of the diluted sample and add 0.6. 6) Take 7.5 ml of 3 M H 2SO4.7.5 ml diphenylcarbazide solution and 4.013 0.022 0.4 ml of 3 M H 2SO4 and 0.66 ml 4.254 0.8. 0.5 diphenylcarbazide Weigh .98 = 300 gm/l ml of 98% concentration H2SO4 300/1.25 gm and dissolve in 100 ml acetone 2) 3 M of 98% concentration H2SO4 3 M = 3 * 98 gm/l = 294 gm/l of 100% H2SO4 294/. 0.833 = 163. 7) Prepare a blank solution by adding 8 ml of 3 M H2SO4.5 ml of the dye and 3. 0.5 ml of distilled water.1 distilled water.5 ml of each of the previous 3 concentrations prepared and add to each one 0. 3) Prepare a blank by adding 0. Analysis procedure 1) Take 1 ml of the sample then dilute it 10 times by adding 9 ml of distilled water in it and stir.01 0.5 ml of distilled water and 0.5 ml of the dye and 3.89 58 . Analysis calculations 1) 1.5 ml of the dye to 11. Calibration curve concentration absorbance 0. 2) Take 7.
518 0.63 0.778 0.05 0.056 0.275 0.107 0.203 0.194 0.708 0.703 0.044 0.1 0.106 0.366 0.28 59 .575 0.071 0.307 0.247 0.736 0.154 0.146 0.305 0.9.529 0.162 0.682 0.065 0.313 0.195 0.678 0.08 0.644 0.725 0.196 0.09 0.492 0.142 0.02 0.762 0.635 0.242 0.491 0.168 0.334 0.308 0.709 0.4.13 0.666 0.287 0.07 0.23 0.255 0.217 0.659 0.438 0. Scanning for iron ions 0 450 475 500 510 520 530 540 550 0 0 0 0 0 0 0 0 0.575 0.06 0.363 0.748 0.337 0.52 0.633 0.409 0.149 0.328 0.147 0.101 0.085 0.487 0.192 0.01 0.442 0.225 0.03 0.229 0.488 0.414 0.603 0.136 0.17 0.588 0.363 0.216 0.04 0.171 0.132 0.09 0.174 0.58 0.
08 0.1 0.06 0.05 0.04 0.242 0.195 0.778 60 .03 0.07 0.725 0.491 0. calibration Abs.659 0.Conc.01 0.363 0.58 0.146 0. 0 0 0.02 0.307 0.09 0.
148 61 .1. Laminar flow Time Absorbance 0 0.309 20 0.199 70 0.226 40 0.258 30 0.183 60 0. Results and discussion 5.176 80 0.22 50 0.343 10 0.5.
2.182 0.117 0. Turbulent flow Time 0 5 10 15 20 25 30 35 40 Absorbance 0.18 0.5.111 62 .122 0.227 0.233 0.276 0.146 0.
06 35 0.173 25 0.5.146 15 0.236 30 0.178 20 0.161 56 0.279 40 0.083 42 0.3.025 14 0.041 21 0.112 49 0.012 5 0.191 v6 turbulent v3 laminar time absorption 0 0. For galvanic corrosion with iron time absorption 0 0 7 0.224 35 0.36 63 .123 10 0.049 28 0.
06 10 0.113 15 0.256 40 0.314 64 .169 30 0.V4 turbulent time absorption 0 0.154 25 0.2 35 0.129 20 0.013 5 0.
6. Conclusion It was concluded that the increase in flow rate increases the rate of reduction of Cr(VI) to Cr(III). Turbulence also increases the rate of reduction. 65 .
Melchers R.. R.2855–2866(2010) 3. Corrosion Science 52 pp. Corrosion Science 52 pp. Parada A. Yi Huang. Journal of Materials Processing Technology 128 pp.49. Peixoto L. Grilli R. “Wear and corrosion behaviour of high-chromium (14–30% Cr) cast iron alloys”..7.. Cabezas C. 375– 380(2008) 2. F. E. Dunn B.. Guang-Ling. “Localized corrosion of a 2219 aluminium alloy exposed to a 3. Watts J. Corrosion Science 52 pp. 2979–2993 (2010) 66 . 455–480(2010) 5.. . “Potential and current distributions of one-dimensional galvanic corrosion systems”. pp. Castle J. Dawei J. Opitz O. Corrosion Science . Sensors and Actuators B 135.. S. 250–255(2002). R. Jeffrey R.... E. A. Garcia A. C. 6. “The changing topography of corroding mild steel surfaces in seawater”. References 1.. pp.5% NaCl solution”. 2270– 2288(2007) 4. Goulart P.. Zumelzu E. “Experimental study on seawater-pipeline internal corrosion monitoring system”. . Goyos I.. “Electrochemical corrosion parameters of as-cast Al–Fe alloys in a NaCl solution”. Baker M.. Osório W..
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