Acknowledgment

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.

Contents
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. It was found that the corrosion rate increase with increasing flow rate for the corrosion of Copper in acidified potassium dichromate. This work is carried out at 30c.

2. Introduction
Corrosion is the destruction metals by interaction with the environment. It doesnt occur also to plastics concrete and wood. 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. Among the metallurgical factors that influence rate of a given metal are composition, internal stresses, and voids, inclusions and dissolve gasses. The environmental factors that influence the rate of corrosion are concentration, electrochemical couples, surface films and stresses. 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.

3. Theoretical Part
3.1. Corrosion Engineering
Corrosion engineering is the application of science and art to prevent or control corrosion damage economically and safely. In order to perform their function properly, corrosion engineers must be well versed in the practices and principles of corrosion: the chemical, metallurgical, physical, and mechanical properties of materials: corrosion testing; the nature of corrosive environments; the availability and fabrication of materials; computers; and design. They also must have the usual attributes of engineers a sense of human relations, integrity, and the ability to think and analyze an awareness of the importance of safety, common sense, a sense of organization, and, of prime importance, a solid feeling for economics. In solving corrosion problems, the corrosion engineer must select the method that will maximize profits. One definition of economics is simply "there is no free lunch." In the past, relatively few engineers received educational training in corrosion. Most of the people then engaged in this field had chemical, electrical, or metallurgical backgrounds. Fortunately this picture has changed. From only three in 1946, now 65 U.S. universities and colleges (including the authors) offer formal courses in corrosion. Corrosion Engineering is a popular textbook for these courses. 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 and even today, corrosion is often regarded as a "necessary evil" to be tolerated. Ignorance is the cause of many premature, unexpected, and expensive failures ignorance even by people who should know better. For example, two vendors of sacrificial anodes describe their systems as anodic protection! Actually it is cathodic protection, which is completely different.

3.2. Nature of Corrosion

Metals, with the exception of the noble metals Cu, Ag, Au, Hg and the Pt metals, are usually found in nature combined with non-metals as oxides, silicates, carbonates, sulphides, etc., and since these have existed in the earth from time immemorial it follows that these compounds, rather than the metal, are the stable form of the metal. To obtain the metal the ore (in which the compound of the metal, or mineral, 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, in which energy is supplied to the system in the form of chemical, 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, 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, in the case of 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 + O2 (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+ + O2 + 2 eIt should be noted that a similar process is used for electroplating zinc, 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; the anodic reaction in this case is the reverse 4

of equation of cathodic reduction, the zinc metal being oxidized to zinc ions. 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. Thus when iron is exposed to an aqueous environment containing dissolved oxygen, which will occur when it is exposed to the atmosphere or immersed in a natural water, it tends to revert to its oxide Fe2O3.H2O, rust, which corresponds in composition to the naturally occurring mineral lepidocrocite. Indeed if metal extraction is regarded as the winning of a metal from its ores for a profit then corrosion is the converse process, i.e. loss of metal and loss of profit.

3.3. Definition of Corrosion

Corrosion is defined as the destruction or deterioration of a material because of reaction with its environment. Some insist that the definition should be restricted to metals, but often the corrosion engineers must consider both metals and nonmetals for solution of a given problem. For purposes of this book we include ceramics, plastics, rubber, and other nonmetallic materials. For example, deterioration of paint and rubber by sunlight or chemicals, fluxing of the lining of a steelmaking furnace, and attack of a solid metal by another molten metal (liquid metal corrosion) are all considered to be corrosion. Corrosion can be fast or slow. Sensitized 18-8 stainless steel is badly attacked in hours by polythionic acid. Railroad tracks usually show slight rustingnot sufficient to affect their performance over many years. The famous iron Delhi Pillar in India was made almost 2000 years ago and is almost as good as new. It is about 32 feet high and 2 feet in diameter. It should be noted, however, that it has been exposed mostly to arid conditions.

Extractive metallurgy is concerned primarily with the winning of the metal from the ore and refining or alloying the metal for use. Most iron ores contain oxides of iron, and rusting of steel by water and oxygen results in a hydrated iron oxide. Rusting is a term reserved for steel and iron corrosion, although many other metals form their oxides when corrosion occurs.

Fig.1 Metallurgy of iron

3.4. Environments
Practically all environments are corrosive to some degree. Some examples are air and moisture: fresh, distilled, salt, and mine waters: rural, urban, and industrial atmospheres: steam and other gases such as chlorine, ammonia, hydrogen sulfide, sulfur dioxide, and fuel gases: mineral acids such as hydrochloric, sulfuric, and nitric: organic acids such as naphthenic, acetic, and formic: alkalies; soils: solvents: vegetable and petroleum oils: and a variety of food products. In general, the "inorganic" materials are more corrosive than the "organics." For example, corrosion in the petroleum industry is due more to sodium chloride, sulfur, hydrochloric and sulfuric acids, and water, than to the oil, naphtha, or gasoline. The trend in the chemical process industries toward higher temperatures and pressures has made possible new processes or improvements in old processes for example, better yields, greater speed, and lower production costs. This also applies to power production, including nuclear power, missiles, and many other methods and processes. Higher temperatures and pressures usually involve more severe corrosion conditions. Many of the present-day operations would

not have been possible or economical without the use of corrosion- resistant materials.

3.5. Other definition of corrosion

Metals are used for engineering constructions because of their mechanical properties, and clearly these are affected by the conversion of the metal into corrosion products, although as will be seen this obviously depends on the rate of corrosion and the extent to which it has proceeded. Metals are also used because of their aesthetic appeal, 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; a black sulphide tarnish on silver is aesthetically undesirable and also has a detrimental effect on properties if the silver is used, for example, as an electrical contact. A precise definition of corrosion is not as simple as might be thought, 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. 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, in others it may be significant but tolerable, while in others it may be so high that its consequences are catastrophic. 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, which in any case requires only a few minutes in a tensile-testing machine. However, the corrosion rate of mild steel obviously depends on the environment and, for example, is far more rapid in an industrial 7

polluted atmosphere than in a clean rural atmosphere it is also more rapid in sea water than in fresh potable water. It follows that the corrosion of a given metal, i.e. the corrosion rate, depends upon the precise environmental conditions to which it will be subjected in service. As far as different metals and alloys arc concerned each has a specific corrosion rate in a given environment; for example, whereas mild steel corrodes rapidly when exposed to an industrial atmosphere, a stainless steel of the type 18Cr-10Ni-3Mo will be virtually uncorroded and its surface remain bright and reflecting. 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, and each environment presents special problems. However, the major application for coatings is for the protection of structures and components that are in contact with natural aqueous environments, which include various atmospheres (industrial, rural, marine; outdoor and indoor exposure) and waters (fresh, brackish, seawater, and polluted water). As far as the atmosphere is concerned it should be noted that, with the exception of the sulphide tarnishing of silver and copper, 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. Contaminants in the atmosphere can markedly affect the corrosion rate, and this applies particularly to gases such as SO2 and H2S and to solid particles such as carbon, NH4C1 and (NH4)2SO4, in general, a polluted industrial atmosphere is far more corrosive than a rural atmosphere. It. should also be noted that the atmospheres in locations near the sea arc contaminated with particles of salt, and this too has a significant effect on the corrosion rate. Different waters vary significantly in (heir corrosiveness; for example sea water is more corrosive than fresh natural waters. How- ever, hard waters 8

(fresh or saline) contain calcium bicarbonate and magnesium sulphate in solution, 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, if deposited on the surface of a corroding metal or within discontinuities in a coating, can act as a barrier that partially isolates the metal from the environment. Similar considerations apply to insoluble corrosion products formed from the metal substrate or metal coating.

3.6. Environments
Practically all environments are corrosive to some degree. Some examples are air and moisture: fresh, distilled, salt, and mine waters: rural, urban, and industrial atmospheres: steam and other gases such as chlorine, ammonia, hydrogen sulfide, sulfur dioxide, and fuel gases: mineral acids such as hydrochloric, sulfuric, and nitric: organic acids such as naphthenic, acetic, and formic: alkalies; soils: solvents: vegetable and petroleum oils: and a variety of food products. In general, the "inorganic" materials are more corrosive than the "organics." For example, corrosion in the petroleum industry is due more to sodium chloride, sulfur, hydrochloric and sulfuric acids, and water, than to the oil, naphtha, or gasoline. The trend in the chemical process industries toward higher temperatures and pressures has made possible new processes or improvements in old processes for example, better yields, greater speed, and lower production costs. This also applies to power production, including nuclear power, missiles, and many other methods and processes. Higher temperatures and pressures usually involve more severe corrosion conditions. Many of the present-day operations would not have been possible or economical without the use of corrosion- resistant materials.

3.7. Corrosion Theory

The search for a better understanding of the actual mechanism has been actively pursued for over a hundred years. We understand what occurs during many corrosion processes, but the search is by no means complete; many areas remain unexplored or litter understood. However, our current knowledge of what takes place during the corrosion process has been sufficient to create effective tools to combat corrosion in most situations. Corrosion is an electrochemical process in which a difference potential develops between two metals or between different parts of a single metal. This voltage can be measured when a metal is electrically connected to a standard electrode. The electrical potential of a metal may be more or less than the standard, in which case the voltage is expressed as either positive or negative. This difference in potential allows current to pass through the metal causing reactions at anodic and cathodic sites. These sites constitute the corrosion cell, as in Figure 2 The anode is the region of lower potential.

Fig.2 Corrosion cell Conversely, the cathode is the region of higher potential. At the anode, metal ions go in to solution. In general the lower the potential of the anode, the

10

greater the amount of metal dissolution and the more serious the corrosion problem. 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. Waters high in dissolved solids are more conductive and cause more severe corrosion problems. Thus, seawaters are generally more corrosive than surface supplies. Any metal immersed in water will soon develop a measurable potential. Those of lower potential can be expected to corrode more easily and extensively than those of higher potential. Theoretically, we can therefore assume that if two metals are coupled, the one of lower potential would become the anode and actively corrode

Fig.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, temperature and velocity; and that in practical situations, the actual conditions may differ. In an actual situation, if a pair of metals of different potential was coupled, 11

problems within the system would probably exit. The result of coupling two metals of closer potential is more difficult to predict. Many other factors must be considered before predictions can be safely made; these are discussed below.

3.8. Corrosion Reactions

It has been demonstrated that potential differences within a metal, or between two metals, will cause chemical reactions at the anode and cathode. Anodic reactions are typified by the dissolution of iron: Fe Fe+2 + 2e Analogous reactions occur in other metals. The electrons migrate through the metal to cathode area where they react in any one of several ways. Some typical cathodic reactions are as follows: a- Hydrogen ion reduction: 2H+ + 2e H2 Important in acidic solutions. b- Reduction of water 2H2O + 2e H2 + 2OH Occurs normally in natural waters. c- Oxygen reduction O2 + 4H + + 4e 2H2O Occurs in aerated acidic solutions. d- Oxygen reduction of water O2 + 2H2O + 4e 4OH Important in natural, aerated waters.

e- Ferric ion reduction Fe+3 + e Fe+2 Occurs under acidic, turbulent conditions (e.g., acid cleaning). f- Sulfate ion reduction 12

4H2 + SO42 S2 + 4H2O Occurs in the presence of sulfate reducing bacteria. g- Metal ion reduction (Plating) M+S + Ne M Involves more noble metals in solution. The most frequent cathodic reactions are a, b, c, and d, negatively changed ions, such as hydroxyl ions produced at the cathodic migrate to the anode of the corrosion cell. Positively charged ions will move toward the cathode. This movement of ions can cause additional reactions at the anode. 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. 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, redrust and hydrated ferric oxide: 2Fe(OH)3 Fe2O3 + 3H2O Fe(OH)3 FeOOH + H2O As solid corrosion products are precipitated at the anode, they may cause the precipitation of other ions from the water. Thus, a corrosion film may show trades of hardness salts, or such suspended matter as mud, sand, silt, clay, or microbiological slime. The structure of the entire surface film, including corrosion products and inclusions, is a major factor in determining the total amount of corrosion products and in the total amount of corrosion which will take place. If a porous can continue, because metal ions can penetrate it and reach the solution interface. If, however, a tight, adherent film is formed, ionic diffusion is 13

prevented and the metal will no longer dissolve. Most corrosion occurs at the beginning of a metals service life. Initially, metal dissolution is not impeded by a film of corrosion products. In time, the film will retard, or halt, the corrosion. The degree to which such a film can impede corrosion is a complex function of the corrosion reactions, the structure of the deposit and the water velocity.

3.9. 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. Understanding the ramifications of the metals aqueous environment and evaluating certain physical aspects of the total system, including the metal structure itself, will provide answers to questions involving such factors as differences in potential between two portions of a metal and the degree of associated corrosion.

3.10. Water Composition:

The nature of the water phase, including dissolved and suspended matter, is integral to the subject of corrosion control. These aspects are discussed briefly to establish general guidelines. The exact constituents of the water phase are unique to any one water supply or application. Therefore, the specific problems encountered in any plants operations are, in a sense, similarly unique. Proper corrosion control requires that each case be considered separately. Often, the treatment program that works well for one plant may fail at a neighboring installation. pH: Between pH 4.3 and 10.0 in natural, aerated waters at normal temperatures, small changes in pH do not seriously affected the degree to which steel is corroded. in the case of ferrous-based materials, the solution just outside the node is mildly alkaline since it is generally saturated with ferrous hydroxide. However, below pH 4.3, where there is free mineral acidity in the water, 14

corrosion progresses rapidly. In this pH range, overvoltage plays a more significant role in the corrosion process. Variations in the macrostructure of the metal or in the water interface become more important. The actual effect of pH on a particular metal is determined by the behavior of its oxide. If the oxide is soluble in acidic media, the metal will corrode rapidly in this environment. If the oxide is readily dissolve in alkaline media, there will be extensive corrosion in the pH range. Most metals falls in to the first category. Occasionally a metal oxide will dissolve in both acid and alkaline solutions; these metals are referred to as amphoteric. The metal will have its greatest stability, from a corrosion standpoint, at some intermediate pH range. Aluminum and Zinc are amphoteric. Their corrosion rates are minimal at pH 6.5 and 11.5, respectively. Some metal oxides are insoluble at any pH. Their corrosion rate will therefore be independent of pH. Noble metals, those at the top of the galvanic series, will behave in this way.

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Fig.4 Variation in corrosion rate with pH value . A number of odd trends are evident in the behavior of iron. As the pH increases to 4.0, the behavior is similar to that of an acid-soluble metal. Between pH 4.3 and 10.0, the corrosion rate is less influenced by pH, because oxygen depolarization is the principle factor determining corrosion. Any further pH increase reduces the corrosion rate, until a minimum value is attained at about pH 12. At this point, iron behaves amphoterically: The corrosion rate again begins to rise with increasing pH. Interestingly enough, this results from hydrogen evolution; iron reacts with strong caustic solutions to liberate hydrogen and form the ferroate ion. Fe +2NaOH Na2FeO2 +H2 Thus we see that hydrogen evolution controls corrosion of ferrous based materials at both extremes of the pH scale.

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3.11. Dissolved salts

The corrosion rate for metals associated with natural, low-solid water, at normal temperature, will accelerate as the concentration of the dissolved salts in the water increases. The corrosion rate may thereafter decrease in more heavily concentrated solutions, as a result precipitation of dissolved salts as their solubility products are reached. In a dilute solution, increased electrical conductivity causes the corrosion rate to increase. For a concentrated solution, precipitation could quite possibly result in a barrier film which would retard corrosion. The ionic constituents in normal waters have various effects on the corrosion rate. For instance, the chloride ion, and to a lesser extent, the sulphate ion are capable of penetrating passive films and setting up highly active, local anodic sites. Conversely, hardness ions and alkalinity have an inhibiting effect on corrosion; the precipitated products of various hardness salts often inhibit corrosion.

3.12. Dissolved Gases

A number of gases are normally found dissolved in water; these include carbon dioxide and oxygen. Other gases may also be present as a result of contamination or other control programs. Three typical examples of these are ammonia, hydrogen sulfide and chlorine. Carbon dioxide The gradual solution of carbon dioxide into water will decrease pH by the formation of carbonic acid. which adds acidity to the water and thereby promotes hydrogen evolution. CO2 + H2O H2CO3 Oxygen The amount of dissolved oxygen in water is directly related to its temperature, pressure, and surface area. Dissolved oxygen in the water acts as a cathodic

17

depolarizer, promoting, corrosion. A special case of oxygen corrosion is mentioned briefly here and discussed later in this chapter. When a water has unequal oxygen concentration, a differential aeration cell is set up. A very common manifestation of this is under-deposit corrosion. Any porous deposit on a metal surface, whether from precipitated salts, suspended matter, or biological growth, will almost always have an oxygen-deficient environment underneath it. This leads to the formation of an active anodic site under the deposit and severe localized corrosion. Ammonia Ammonia is generally introduced in to water as a result of process contamination. It will selectively corrode copper in the presence of oxidizing agents. NH3 + H2O NH4OH NH4OH + Cu+2 Cu (NH3)+2 +H2O This soluble copper-ammonium complex is very corrosive to copper. Hydrogen sulfide Hydrogen sulfide is one of the most harmful gases that can enter a cooling water system. It normally results from process contamination. Especially in refineries and petrochemical plants, or is produced by the reduction of sulfate ions by sulfate-reducing bacteria. The gas promotes active corrosion in two ways. Because it is acidic, it causes low pH attack. Secondly, it is responsible for the formation of iron sulfide which is cathodic to iron and leads to galvanic corrosion. Chlorine Chlorine gas is the most commonly used toxicant for the control of micro organisms in cooling water systems. Upon entering the water, it hydrolyzes to form hypochlorous and hydrochloric acid. This action reduces the pH of the recirculating water and causes increased corrosion. On many metals it also 18

retards formation of certain protective corrosion inhibitor films. Suspended matter Mud, sand, clay, dirt and other particles may enter a cooling water system either as airborne contamination or as part of the systems makeup water supply. In areas of the system where sedimentation of these materials take place. Porous deposits are easily formed and differential aeration cells are quickly established, which can cause more corrosive damage than precipitated salts. Microorganisms Microorganisms' growth often presents very special problems, Hydrogen is metabolized by many species. Causing depolarization of the corrosion cell, similar to the action caused by dissolved oxygen. Anaerobic bacteria form differential aeration cells and accelerate local attack. Some species produce acidic compounds. Desulfovibrio desufuricans, a type of sulfate-reducing bacteria. Produced hydrogen sulfide by reduction of the sulfate ions found in almost all water supplies. Such sulfate oxidizers as the Thiobacillus oxidize the sulfate ions to sulfuric acid and cause low pH attack. Physical Factors A systems design and operating characteristics are often determining factors at the onset and continuance of corrosion. 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. The existence of an anode merely indicates that there is a potential for corrosion current it does not determine the rate of corrosion. This is governed by other factors such as the relative areas of the cathode and anode. 19

The rate of corrosion increases in proportional to the ratio of cathodic area to anodic area. In the evaluation of a nickel-steel couple. For example, the galvanic series indicates that the nickel is cathodic to steel. 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. Reversing the situation results in far less corrosion of steel between the ratio of cathodic to anodic area is small. The effect of relative areas also applies to a single metal. 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. The relative-area effects become more important as the conductivity of the solution increase. In dilute solutions, only the cathodic area immediately around the anode is important, because the solutions conductivity is low. In brackish water or seawater, relative area effects are extremely important. Temperature: The extent of corrosion increases with temperature. For example, in a domestic water system, a rise in temperature from 60F to 176F may increase corrosion as much as 400 percent. An increase corrosion in inhibitor levels would consequently be necessary to minimize this problem. In general, as temperature rises, diffusion increases, and both overvoltage and viscosity decrease. Increased diffusion enables more dissolved oxygen to reach a cathodic surface, thereby depolarizing the corrosion cell. Overvoltage decreases causing depolarization by hydrogen evolution. A decrease in viscosity aids both depolarization mechanisms because it favors solution atmospheric oxygen and enhances hydrogen evolution. In an open system, corrosion rates increases with rise in temperature, deposit the decrease in the solubility and availability of dissolved oxygen, because diffusion rates have also increased. The net effect is an increase in the amount of dissolved oxygen reaching the metal surface. This trend continuous until 20

about 170F, when the dissolved oxygen exceeds the amount made available by diffusion. In a closed system, 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; a conditions which explains active corrosion in systems subjected to unequal heat transfer, and a problem often experienced in fouled heat exchangers. This is shown in figure (6). Some metals or alloys change their electric potential as temperature rises. The zinc coating on galvanized steel be comes cathodic to the ferrous portion at about 150F and no longer provides corrosion protection. Heat transfer Heat transfer surfaces such as those in cooling water systems are particularly difficult to protect. This is attributed to high skin temperatures along the metal surface. 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, as shown in Fig .

Fig.5 Galvanic cell caused by difference in temperature

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Velocity There are two categories of water flow laminar and turbulent. Laminar flow is low in velocity and may not be consistent across the metal surface. Turbulent flow is at a rate and distribution nearly that of plug flow (maximum velocity turbulent flow). These are shown in Fig .Even in turbulent flow, however, there is a thin, laminar film of water along the metal surface; the greater the turbulence, the thinner the laminar layer. 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. As velocity (turbulence increases, the depth of the laminar zone decreases and more oxygen can reach the metal surface. In addition, high velocity waters remove what might have become a passivating layer as corrosion product, producing the net effect of accelerated corrosion. Figure (?) illustrates this effect graphically using corrosion in a condenser tube as an example.

Fig.6 Velocity distribution in laminar and turbulent flow. (a) Low velocity laminar flow (b) High velocity turbulent flow (c) Very high velocity turbulent flow For inhibited water there is a compensating factor. As oxygen diffusion to the metal surface increases, so does inhibitor diffusion. Therefore, less corrosion inhibitor is required at higher velocities conversely, cooling water systems in a standby condition, or low velocity areas in a cooling systems e.g., shell side water flow heat exchangers are difficult to protect at normal inhibitor levels.

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Dissimilar metals: Any metal coupled to one above it will become the anode. If a galvanic cell is set up by the coupled metals, hydrogen will be reduced on the cathodic metal and absorbed on its surface. The extent of corrosion is determined by many of the factors discussed in the previous section, relative areas, solution conductivity and relative areas, solution conductivity and polarization mechanisms being the most important. If the ratio of cathodic to anodic surfaces is low. Galvanic corrosion will be limited. Solutions of low conductivity also limit galvanic attack because only the immediately adjacent cathode areas are associated with the anode, 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. In the design of equipment where galvanic corrosion may be a problem, dissimilar metals should be separated by a non-conductive substance such as a dielectric union, plastic sleeve or insert. Galvanic cells may be used to advantage to protect a given metal. In many situations, iron is protected by coupling it to a less noble metal such as magnesium. In such a cell, the iron becomes the protected cathode and the magnesium the scarified anode. Mechanical effects Corrosion can often be initiated or intensified by the conjoint of mechanical factors. Typical examples include the presence of inherent or applied stresses. Fatigue, fretting or cavitation effects. Inhibitors that are effective in the absence of some or all of these phenomena may not be so in their presence. In fact it may not always be possible to use inhibitors successfully in their situations and methods of corrosion prevention will be required.

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Metallurgy: Metals are never absolutely flat, plane structures. All have surface flaws such as scratches, in which the potential for electron loss and metallic ion formation increases. Those areas will become anodic in the rest of the metal. A stressed metal would normally set up anodic sites at certain intergranular boundaries. Anodic site formation may result from a number of causes detectable under microscopic inspection. 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. Two adjacent grains of different density might create a corrosion cell. Precipitation at metal grain boundaries will cause a corrosion cell to form, especially if the precipitates more noble than the metal itself. An increase in metal purity provides no guarantee that corrosion will decreased. Aluminum and iron may serve as example of constructing behavior. Aluminums resistance to corrosion increases as its purity does. He resistance of iron remains the same as its purity increases. Pure iron is the more resistance to corrosion than cast iron or steel. In the case of aluminum, corrosion protection depends upon the formation of oxide films, which is aided by increases in purity. For iron, the controlling factors are the corrosion reactions themselves.

3.13. Combating Corrosion

The following items should be considered as means of combating corrosion. 3.13.1. Select Proper Material The most common method of preventing corrosion is the selection of the proper metal or alloy for a particular corrosive service. Since this is the most important method of preventing or reducing corrosion damage. One of the most popular misconceptions to those not familiar with metallurgy or corrosion engineering concerns the uses and characteristics of stainless steel. Stainless steel is not stainless, it is not the most corrosion-resistant material, and it is not a specific alloy. Stainless steel is the generic name for a series of more than 30 24

different alloys containing from 11.5 to 30% chromium and 0 to 22% nickel, together with other alloy additions. Stainless steels have widespread application in resisting corrosion, but it should be remembered that they do not resist all corrosives. In fact, under certain conditions, such as chloride-containing mediums and stressed structures, stainless steels are less resistant than ordinary structural steel. Stainless alloys are more susceptible to localized corrosion such as intergranular corrosion, stress-corrosion cracking, and pitting attack than ordinary structural steels. Frequently, the quality of stainless steels is checked with a magnet. This is based on the belief that nonmagnetic stainless steels represent "good" alloys, and stainless steels that are magnetic are inferior. This test has no basis and, in fact. is misleading. Many stainless steel alloys are magnetic, and many of the cast austenitic stainless steels show some ferromagnetic properties. There is no correlation between magnetic susceptibility and corrosion resistance. Under certain conditions many of the magnetic stainless steels are superior to the nonmagnetic varieties. In summary, 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." Stainless steels represent a class of highly corrosion resistant materials of relatively low cost that should be carefully used. In alloy selection, there are several "natural metal-corrosive combinations. These combinations of metal and corrosive usually represent the maximum amount of corrosion resistance for the least amount of money. Some of these natural combinations are as follows: 1. Stainless steels-nitric acid 2. Nickel and nickel alloys-caustic 3. Monel-hydrofluoric acid 4. Hastelloys (Chlorimets)-hot hydrochloric acid 25

5. Lead-dilute sulfuric acid 6. Aluminum-nonstaining atmospheric exposure 7. Tin-distilled water 8. Titanium-hot strong oxidizing solutions 9. Tantalum-ultimate resistance 10. Steel-concentrated sulfuric acid The above list does not represent the only material-corrosive combinations. In many instances, cheaper materials or more resistant materials are available. For nitric acid service, the stainless steels are usually considered first, 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. For many years, tantalum has been considered and used as an "ultimate" corrosion-resistant material. Tantalum is resistant to most acids at all concentrations and temperatures and is generally used under conditions were minimal corrosion is required, such as implants in the human body. An interesting feature about tantalum is that it almost exactly parallels the corrosion resistance of glass. Both glass and tantalum are resistant to virtually all mediums except hydrofluoric acid and caustic solutions. For this reason, manufacturers of glass-lined equipment use tantalum plugs to seal defects since this material matches the resistance of glass. There are some general, but usually accurate, rules that may be applied to the resistance of metals and alloys. For reducing or nonoxidizing environments, such as air-free acids and aqueous solutions, nickel, copper, and their alloys are frequently employed. For oxidizing conditions, chromium-containing alloys are used. For extremely powerful oxidizing conditions, titanium and its alloys have shown superior resistance.

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3.13.2. Proper Design Design considerations, with respect to minimizing corrosion difficulties should, include the desirability, 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. Butt joins should be used wherever possible. If lap joints employing fillet welds are used the welds should be continuous on the process side. 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 , consideration should be given to insulating then from each ether making anodic material area as large as possible , equipment should be supported in such a way that it will net rest in pools of liquid or on damp insulating material , porous insulation should be weatherproofed or otherwise protected from moisture and spills to avoid content of the wet material with the equipment , 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 , inspection during fabrication and prior to acceptance is desirable . 3.13.3. Alter Environment Simple changes in environment may make an appreciable difference corrosion of metals and should be considered as a means of combating corrosion . Oxygen is an important factor and its removal or addition may cause marked changes in corrosion, the treatment of boiler feed water for instance to remove oxygen greatly reduces the corrosiveness of the water on steel . 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

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 . Reduction in temperature will almost always be beneficial with respect to reducing corrosion. Reduction in velocity and turbulence will generally result in reduced corrosion an exception being where solids may collect on surface and case pitting. 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 , 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 . Elimination of moisture can and frequently does minimize , if not prevent corrosion of metals and this possibility of environment alteration should always be considered .

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

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Fig.7 Schematic summary of the various forms of corrosion. noble potential in the Galvanic Series. At the same time, the more noble alloy Uniform corrosion accounts for the greatest tonnage of metal consumed. 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). Any alloy will be preferentially corroded when coupled to another alloy with a more positive or is protected from corrosion. The negative, preferentially corroded alloy in the couple is said to be active in the Galvanic Series.

3.14. Crevice Corrosion

Corrosion of an alloy is often greater in the small sheltered volume of the crevice created by contact with another material. The second material may be part of a fastener (bolt, rivet, and washer) of the same or a different alloy, a deposit of mud, sand, or other insoluble solid, or a nonmetallic gasket or packing. Crevice corrosion seems to be the preferred title for metal-metal crevices. Deposit corrosion and gasket corrosion are terms sometimes used when a nonmetallic material forms a crevice on the metal surface. If the crevice is made up of differing alloys or if the deposit is conductive (e.g., magnetite or

29

graphite), crevice corrosion may be compounded by galvanic effects.

Fig.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, while the outer surfaces can drain and dry. Thus, the bolt in figure was heavily corroded within the crevice as compared to the outer surfaces.

Fig.9 Corrosion of steel bolt in an industrial environment resulting from continually wetted area within a crevice 30

Crevice corrosion of stainless steels in aerated salt solutions is widely known. Corrosion products of Fe, Cr, and Ni, the main components of stainless steel, accumulated in the crevice and form very acid chloride solutions in which corrosion rates are very high. 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.

Fig.10 crevice corrosion of drilled and tapped stainless steel test specimen in 3% NaCl solution at 90C

3.15. Pitting corrosion

Localized attack in an otherwise resistant surface produces pitting corrosion. The pits may be deep, shallow, or undercut, as shown in figure (8). 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. Pitting shares the same mechanism with crevice corrosion in stainless steels. The pit is a self-serving crevice that restricts transport between the bulk solution and the acid chloride pit anode. Standard exposure and

31

electrochemical testing methods are described, as well as the electrochemical theory behind crevice and pitting corrosion.

3.16. 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). Three related but distinct types of failure are included in EIC: stress corrosion cracking (SCC), corrosion fatigue cracking (CFC). And hydrogen-induced cracking (HIC). Alternative terms for HIC are hydrogen embrittlement. Hydrogen-assisted cracking, and hydrogen stress cracking. Stress corrosion cracking occurs in alloys with a static tensile stress in the presence of specific environmental conditions. Pure metals are comparatively resistant to stress corrosion cracking. A passive surface film under oxidizing conditions must be present, and corrosion rates are consequently quite low. A specific dissolved species is often required. For example, stainless steels are susceptible in hot chlorides. Brass in ammonia solutions, and carbon steel in nitrates. Further discussion of critical environments for most of the important constructional alloys are summarized in different tables. Figure shows an example of stress corrosion cracking in a U-bend test specimen.

Fig.11 Stress corrosion cracking at a U-bend .

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Corrosion fatigue cracking occurs under cyclic stresses in a corrosive environment. Susceptibility to and rate of fatigue cracking without corrosion are usually increased in the presence of a corrosive environment. Both alloys and pure metals are susceptible, 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. However, beach marks may also be caused by differences in microplastic deformation when crack propagation is interrupted, and beach marks may be present with little or no visible corrosion. 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, 2H+ + 2e- H2 produces atomic hydrogen at the surface during corrosion, electroplating, cleaning and pickling, or cathodic protection. Although stress corrosion cracks often show more branching, cracks have a very similar appearance otherwise. However, hydrogen induced cracking is accelerated by cathodic polarization, whereas stresses corrosion cracking and corrosion fatigue cracking are suppressed.

Fig.12 Beach marks on the fracture surface of a fatigue failure . Hydrogen induced cracking usually predominates over stress corrosion

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cracking in carbon and low alloy steels, stainless steels, aluminum alloys, and titanium which have been alloyed, heat treated, or cold worked to near maximum strength. Hydrogen induced cracking also contributes to losses of fatigue life in such strength alloys, 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. Other effects at higher hydrogen levels are usually irreversible. Hydrogen attack is the reaction of hydrogen with carbides in steel to form methane, resulting in decarburization. Voids, and surface blisters. Hydrogen blisters or smaller hydrogen cracks become evident when internal hydrogen-filled voids erupt at the surface. Voids are formed when atomic hydrogen migrates from the surface to internal defects and inclusions, where molecular hydrogen gas can nucleate, generating sufficient internal pressure to deform and rupture the metal locally. Hydride formation embrittles reactive metals such as titanium, zirconium, magnesium, tantalum, niobium, vanadium, uranium, and thorium. The other hydrogen damage mechanisms described are also possible in these metals.

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Fig.13 Hydrogen blister in AISI 1020 carbon steel

Intergranular Corrosion Reactive impurities may segregate, or passivating elements such as chromium may be depleted at the grain boundaries. As a result, 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. Thus, intergranular corrosion (IGC), sometimes called intergranular attack, is a common problem in many alloy systems. 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. The resultant structure is susceptible or sensitized to IGC. In the temperature range 425 to 815C (800 to 1500F), chromium carbides (mainly Cr23C6) precipitate at the grain boundaries, depleting the grain boundary and nearby structure of chromium. 35

Below about 10% Cr, these areas lose resistance and are corroded referentially. Figure shows an example of intergranular corrosion of sensitized austenitic stainless steel.

Fig.14 intergranular corrosion of a sensitized stainless steel surface viewed by scanning electron microscopy. Dealloying and Dezincification An alloying element that is active (negative electrochemically) to the major solvent element is likely to be preferentially corroded by dealloying. Selective leaching and parting area alternative terms used occasionally for the same phenomenon. The deal loving of brass, known as dezincification, is a common and frequently cited example. Zinc is strongly active to copper (Table 1) and readily leaches out of brass, leaving behind relatively pure porous copper with poor mechanical properties. Uniform or layer dezincification is easily recognizable by the red, copper-colored material visible on the bolt surface in Figure . The deformed bolt, previously ex posed to acidic cooling tower waters, shows a weak, brittle layer of uniform thickness. In plug dezincification the attack is localized and results in penetration and weakening of brass pipe and tubing. Dezincification often occurs under deposits and in other nonvisible locations, and failures may be sudden and unpredictable. Copper is the most noble of the major constructional metals, and selective leaching of other more 36

active alloying elements, such as nickel, silicon, and aluminum has also been reported.

Fig.15 Brass bolt (30% Zn) which was bent to shoe uniform penetration of a dezincified layer. The other major example of dealloying, known as graphitic corrosion, is the elective leaching of iron from gray cast iron, leaving behind a weak, porous network of inert graphite that can be scratched with a pen knife as shown in figure (16). Graphitic corrosion has occurred primarily in buried cast iron pipe and becomes evident only after decades of service. When the old graphitized pipe is disturbed, escaping hazardous chemicals can contaminate the surrounding soil or cause fatal explosions and fires.

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Fig.16 Graphitic corrosion in a gray cast iron water pipe. Erosion-Corrosion and Fretting Recombination of a corrosive fluid and high flow velocity result in erosioncorrosion. The same stagnant or slow-flowing fluid will cause a low or modest corrosion rate, but rapid movement of the corrosive fluid physically erodes and removes the protective cohesion product film, exposes the reactive alloy beneath, and accelerates corrosion. 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. The attack generally follows the directions of localized flow and turbulence around surface irregularities. Figure shows characteristics horseshoe-shaped pits whose ends follow the downstream flow pattern in copper and brass condenser tubes. Harder alloys (brass and bronze) are more resistant, but the chemical component of the mechanism is evident by the dependence on composition of the flowing corrosive solution. Alloying elements such as aluminum and nickel, which form tighter, more adherent surface films, also improve resistance. Erosioncorrosion is a common problem in steel pipe with flowing steam carrying condensate water droplets.

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Fig.17 Brass condenser tube showing erosion corrosion in salt water. Cavitation is a special case of erosion-corrosion. It occurs where velocity is so high that pressure reductions in the flow are sufficient to nucleate water vapor bubbles, which then implode (collapse) on the surface. The implosions produce extreme pressure bursts that disrupt surface films and even dislodge particles from the metal itself. The attack takes the form of roughened pits, which may eventually result in penetration, as in Figure (20). Cavitation occurs on turbine blades, pump impellers, ship propellers, and in tube and pipe where large pressure changes are present. Although largely mechanical, the chemical and electrochemical contributions are apparent in benefits from selection of corrosion-resistant alloys and control of solution composition. Fretting is another type of erosion-corrosion, but in the vapor phase. The erosion is provided by repeated by repeated small movement, often from vibration, between the corroding metal and another contacting solid under load. The motion abrades surface oxide film off the metal surface, again exposing the reactive metal to increased oxide formation. The effect is compounded by the oxide debris, which acts as an additional abrasive between the contacting surfaces. A fine red rouge of iron oxide particles is produced on steel.

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Fig.18 Cavitatior of the cast iron suction bell from a low water pump.

3.17. 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, it must have a negative free-energy change (G). For electro-chemical react ions: G = -ZFE (5)

where n is the number of electrons involved in the reaction, F is the Faraday constant, and E is the cell potential. For the reaction to be feasible (G is negative), the cell potential E must be positive.

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Table 1 Standard Oxidation-Reduction Potentials Au Au+++ + 3eO2 + 4H+ + 4e- 2H2O Ag Ag+ + eFe+++ + e- Fe+ O2 + 2H2O + 4e- 4OHCu Cu++ + 2e2H+ + 2e- H2 Ni Ni++ + 2eFe Fe++ + 2eCr Cr+++ +3eZn Zn++ + 2eAl Al+++ + 3eNa Na+ + e+1.498 +1.229 +0.799 +0.771 +0.401 +0.337 +0.000 -0.250 -0.440 -0.744 -0.763 -1.662 -2.714

Volts versus normal hydrogen electrode at 25 C. What is the cell potential? First, we must consider the separate anode and cathode reactions. If a solid piece of iron is placed in a solution containing iron ions, a potential difference, E [Fe/ Fe++], exists between the iron atoms in the solid and the iron ions in solution. This potential can be measured with a voltmeter by connecting it to an inert reference electrode placed in the solution. This potential is called a half-cell potential because it is for an electrode that can form half (i.e.. the anode) of a corrosion cell. Similarly, a half-cell potential exists for the cathode reaction. A measured half-cell potential depends on the concentration of the ions in solution. If metal ions are present in the amount of 1 gram atom (i.e. unit activity), the half-cell potential is called standard Half-Cell potential. If the latter is known then the half-cell potential at any concentration can be calcu41

lated from the Nernst equation. By convention, the hydrogen reaction, 2H+ + 2e- H2; is assigned a standard half-cell potential of zero volts. All other half-cell potentials are measured relative to that of hydrogen. These potentials are also called oxidation-reduction potentials (redox potentials) because they represent oxidation or reduction reactions depending upon the direction. For example, Fe+++ + e- Fe++ is a reduction reaction, while Fe++ Fe+++ + e- is oxidation. The electrode potential for each of these reactions is numerically the same. The cell potential E that is used in the free-energy change equation, Eq. (1), is defined as the potential difference between the cathode and anode half-cells. For the example of iron in acid solutions: E = E [H+/H2] E[Fe/Fe++] E = 0 (-0.440) = +0.440 v (1) Since E is positive, G in Eq. (5) is negative, and the reaction is feasible. Likewise, for iron in neutral water: E = E [O2/OH-] E[Fe/Fe++] E = +0.401 (-0.440) = +0.841 v) The reaction is feasible because G in Eq. (5) will be negative. This is actually the rusting of iron in moist air. If we consider gold in hydrochloric acid, what will happen? Could it corrode and give hydrogen? The cell potential for this reaction would be: E = 0 - 1.498 =-1.498 v. The reaction is impossible because G in Eq. (1) would be positive. This conclusion is true for all metal/ metal-ion combinations with redox potentials that arc more positive than hydrogen's.

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How fast will corrosion happen? To determine the thermodynamic feasibility of a certain corrosion reaction, we have considered the behavior of independently operating anodes and cathodes with no current passing between them. 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, then the potentials of the anode and cathode would remain the same (i.e., at their half-cell level). In this condition, the current would be zero (Ohms law, I = E/R), and no corrosion would occur. At the other extreme, if the resistance were zero, the current would be infinite, and we would have instant and total corrosion. In practice, the resistance approaches zero, which results in a maximum Unite current. When current flows between the anode and cathode, the potentials of both change. This change is called polarization. Polarization reduces the potential difference between anode and cathode areas (i.e., driving force for the reaction decreases) as shown in Fig. The current flowing between the anode and cathode at any point is given by: i' = (Ec Ea)/R films), Ec and Ea are the cathode and anode potentials, respectively. (6)

Where R is the total resistance of the circuit (metal, solution, any surface

Fig.19 Polarization for iron in acid solution

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Because the anodes and cathodes are usually very closely spaced, R is small. Therefore, for a finite maximum current, Ec Ea must be small, and the point of intersection of the curves (Fig. 3) is a good estimate of the conditions existing during corrosion. Actually, the true conditions are slightly to the left of the point of intersection, in order to maintain the small potential difference between anode and cathode areas, which drives the current through the circuit. Once a metal has come to equilibrium in its corrodent, and is corroding freely, it will have a corrosion potential Ecorr, and a corrosion current density between anode and cathode areas of icorr. Corrosion potential (Ecorr) can be easily measured experimentally with the setup shown in Fig. 3. We arc measuring the potential difference between a corroding metal and its ions in solution. The corrosion potential should not be confused with the previously discussed thermodynamic quantity, cell potential. Corrosion current density can be converted to a corrosion rate by using Faraday's laws. Rmpy = 0.13 Ie/ Where Rmpy is corrosion rate, mils/yr.; I is current density, microamp./sq. cm.; e is equivalent weight (chemical) of the metal, g.; and is density of metal, g./cu.cm.

Methods of measuring the current density will be described in the next article.

3.18. Polarization
It is very important to understand the significance of polarization. Polarization diagrams of the type shown in Fig. will be used throughout this series. We have defined polarization as a change in the potential of an electrode as current flows to or from it. For a given current flow, this change may be small or large as shown in Fig. 4a. As the degree of polarization increases, the rate of corrosion decreases. The polarization on the anode may be less than, or greater

44

than, that on the cathode as seen in Fig. 4b and 4c. For simplicity, we shall use the mixed polarization case shown in Fig. 4a in most of our examples. (The actual curves are not necessarily straight lines as shown in the sketches.)

Fig.20 effect of polarization on electrodes Before describing the different types of polarization, we shall consider a specific example. When iron corrodes in hydrochloric acid, hydrogen ions are reduced at the cathode to form hydrogen gas. The molecule of hydrogen is no longer needed by the corrosion reaction. In fact, it is in the way it stays in the cathode area, because it prevents other hydrogen ions from reaching the metal surface and reacting. Hydrogen gas can therefore retard, or polarize, the cathode operation. The situation is shown in Fig. 5. In this conation, corrosion will continue but more slowly than it could if the molecules of hydrogen gas were rapidly moved away. Metals, with the exception of the noble metals Cu, Ag, Au, Hg and the Pt metals, are usually found in nature combined with non-metals as oxides, silicates, carbonates, sulphides, etc., and since these have existed in the earth from time immemorial it follows that these compounds, rather than the metal, are the stable form of the metal. To obtain the metal the ore (in which the compound of the metal, or mineral, is present in a suitable form and at a

45

sufficient concentration for its conversion to the metal to be technologically and economically feasible) is subjected to a reduction process, in which energy is supplied to the system in the form of chemical, 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, 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, in the case of 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 + O2 (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+ + O2 + 2 eIt should be noted that a similar process is used for electroplating zinc, 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; the anodic reaction in this case is the reverse of equation of cathodic reduction, the zinc metal being oxidized to zinc ions. 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. This sequence of events in which the mineral is reduced to the metal, with a consequent increase in energy, and the subsequent spontaneous conversion of the metal back to a compound 46

(referred to as a corrosion product, which frequently has the same composition and crystal structure as the mineral) with a decrease in energy is illustrated in figure .

Fig.21 Diagrammatic representation of the energy changes that take place during the chemical reduction of a mineral (hematite, Fe2O3 .H2O) to the metal
3

(iron), 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, which will occur when it is exposed to the atmosphere or immersed in a natural water, it tends to revert to its oxide Fe2O3.H2O, rust, which corresponds in composition to the naturally occurring mineral lepidocrocite. Indeed if metal extraction is regarded as the winning of a metal from its ores for a profit then corrosion is the converse process, i.e. loss of metal and loss of profit.

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3.19. Corrosion in Acids

Metal Dissolution: Considered the surface of the metal M contained in a vacuum. 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. This gas helps to coment the position ions together and gives the metal its special properties. If sufficient energy is available about (600 kJ/mol) it will be possible to pull on ion out of its energy well in the surface, so forming a highly unstable gaseous metal ions M+Zc which exert a restoring force on the ion. One ways of generating hydrogen in a laboratory is to place zinc into a dilute acid, such as hydrogen chloride or sulfuric. Zn + 2 HCL ZnCl2 + H2 Zn + H2SO4ZnSO4 + H2 This equation complete chemical reaction and are balanced. 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, the anodic reaction always is the oxidation of metal to a higher valance state. The above reaction involves the reduction of hydrogen ions to hydrogen gas according to the reaction. 2 H+ + 2e- 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, open vessel) and 1.5 to 2.5 MPy in concentrated acid.

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The corrosion rate in another than dilute solutions increases with hydrochloride acid concentration. Hydrochloric acid similar sulphuric acid in corrosion properties because it non oxidizing acid. This acid will actively attack many metals with direct replacement of hydrogen gas where this happens the rate of corrosion is rapid. Hydrochloric acid is the most difficult of the common acids to handle from the standpoints of corrosion and materials of construction. Extreme care is required in the selection of materials to handle the aid by it self, even in relatively dilute concentrations, or in process solutions containing appreciable amounts of hydrochloric acid. This acid is very corrosive to most of the common metals and alloys. When aeration or oxidizing agents are also present, corrosive conditions may be very rugged. Many unexpected failures in service are explained by the presence of ostensibly minor impurities. The commercial or muriatic acid often behaves very differently from the chemically pure or reagent grade hydrochloric acid as far as corrosion is concerned. More and more so-called by-product acid is appearing on the market and being used in the process industries. These by-product acids could contain any number of impurities, depending on the present process. Almost invariably some iron is present, and ferric chloride is often a destructive pitting agent. In fact, 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. The limits for so-called acceptable corrosion rates are usually raised when considering materials of construction for handling hydrochloric acid. Materials that show very low rates of corrosion are often not economically feasible. Good judgment is required to obtain a good balance between service life and cost of equipment. Where contamination is a problem, expensive materials such as tantalum are the only ones that can be utilized. Metals and alloys are placed in three classifications: 49

(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.

3.20. Metals and Alloys

Ordinary carbon steels and cast iron are never used for hydrochloric acid service. Rapid corrosion occurs at pH 4 or 5 or below, particularly if appreciable solution velocities are involved. Aeration or oxidizing conditions result in destructive attack, even in very dilute solutions. Inhibitors are required when iron and steel equipment is cleaned by pickling with hydrochloric acid. Zinc and magnesium are rapidly attacked by this acid. Tin and tin plate are used for solutions containing small amounts of acid such as food products. Aeration is also destructive to tin.

3.21. 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. 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. These figures are somewhat misleading because zero corrosion assumed as the base line is unattainable. Some measures while reducing corrosion will cost more than the parts or equipment protected. 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. Nevertheless the economic costs of corrosion are obviously enormous. 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. 50

Loss of Product Leaking container, tank and pipeline result in significant loss in product, which have a high cost. 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. 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. 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. Human life and safety Corrosion takes an even more significant toll in human life and safety. Corrosion is never correctly reported as the cause of many fatal accidents, but a few examples can be cited readily. The airline accident in Hawaii has already been mentioned. The well-known bridge collapse at pt pleasant west Virginia killed 46 in 1967 and has been attributed to stress corrosion cracking. These are only a few examples of the many such fatal accidents caused by corrosion.

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3.22. Literature survey

HuangY., Dawei Jstudied, a CuZn galvanic sensor is developed for the internal-pipeline corrosion on-line monitoringsystem, in which the internalpipeline corrosion state is grasped based on monitoring the corrosion capability of the internal electrolyte environment. The galvanic corrosion behaviors of the sensor in a simulatedseawater environment are investigated using a 50-m-long pipeline in the laboratory. After long-term testand analysis, theeffective working period of the sensor is confirmed, 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. A complex and non-linear relationship, among theelectric current of the galvanic sensor, flow rate and temperature of the electrolyte, the concentrationof dissolved oxygen (DO) in pipeline, is acquired. Finally, 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,flow rate and temperature of the internal electrolyte. Based on the comparison between corrosion coupons test and monitoring system, it is affirmed that amore reasonable evaluation of internal-pipeline corrosion can be proposed in the monitoring system. Grilli R., et al ;This work is focused on the role of intermetallics in pitting corrosion of Al2219 alloy. Second phase particleswere characterized by AES, SAM and EDX. Their behavior in a solution of NaCl was investigated asa function of exposure time. The results confirmed the cathodic nature of the intermetallics with respectto the aluminum matrix. Corrosion products rich in aluminum and oxygen were found to progressively accumulate around the particles and iron was dissolved from the intermetallic, followed by back deposition. Copper and manganese did not show any major activity. After 32 h of exposure 52

the largerintermetallics were completely covered. JeffreyR., Melchers R. E. studied the corrosion of mild steel exposed to marine immersion conditions typically is not uniformalthough it is often idealized as such. 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. The present paper presentsa number of images typical of the sequential evolution of the surface topology of mild steelcorroding in subtropical coastal seawater. The sequence consists of the development of anodicareas, development of small pits and shallow broad pits, the apparent coalescence of small pits into larger localized corrosion and eventually the appearance of stepped or benched, perhaps irregularshapedbroad or macro-pits. 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. 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. Song G. L., Many practical galvanic corrosion problems can be simplified into a one-dimensional mathematical equation. In this study, 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. The developed analytical approach is then applied to some practical galvanic corrosion cases, such as a steelAl joint exposed to bio-fuel E85, a galvanic couple separated by a passive spacer and a scratched organic coating. 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.

53

Zumelzu E. et al, High-chromium (1430%) cast iron alloy samples, with variations in the carbon and nickel content, were prepared in order to study theirhardness, resilience, corrosion resistance, and wear behavior by means of simulating the conditions found at the sugar industry processes. 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. Chemical analyses were carried out using atomic absorption to evaluate the deterioration with regard to the attack to chemical composition of alloys, wear, ionic solutions, and the micro structural changes undergoneby the different alloys employed. The behavior of alloys to wear and corrosion depends mainly on the chemical composition and effect of the alloying elements, the formation of carbides during solidification, and the presence of impurities and inclusionsat a surface level. The results obtained in this study made possible the selection of better alloys, which can be employed at the sugar industry, such as 0.97C29.5Cr1.84Ni which has high chromium content. OsrioW. R., aim to evaluate the general electrochemical corrosion resistance of AlFe alloys in the range of hypoeutectic compositions, Al0.5 wt. % Fe and Al1.5 wt. % Fe alloy. EIS plots, potentiodynamicpolarization curves and an equivalent circuit analysis were used to evaluate the electrochemical parameters in a 0.5 M NaCl solution at 25 C. It is shown that for an Al0.5 wt. % Fe alloy, coarse cells tend to improve the corrosion resistance mainly due to the reduction in cellular boundaries and for an Al1.5 wt. % Fe alloy, an opposite trend has been detected.

54

4. Experimental Part
4.1. Apparatus

(1) Tank (3) Copper tube (5) Recycle valve (7) Mechanical stirrer

(2) Pump (4) Tank (6) Feed valve

55

56

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 = 1.833 gm/ml 800/1.833 ~ 436 ml 3) The rest of 8 l is distilled water

4.4. Procedures
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.

57

2) Measure 7.5 ml of the solution then add 0.5 ml of 3 M H 2SO4, 0.5 ml of the dye and 3.5 ml of distilled water. 3) Measure 4 ml of the solution then add 4 ml of 3 M H2SO4. 4) Measure 2 ml of the solution then add 6 ml of 3 M H2SO4. 5) Measure 1 ml of the solution then add 7 ml of 3 M H2SO4. 6) Take 7.5 ml of each of the previous 3 concentrations prepared and add to each one 0.5 ml of 3 M H2SO4, 0.5 ml of the dye and 3.5 ml of distilled water. 7) Prepare a blank solution by adding 8 ml of 3 M H2SO4, 3.5 ml of distilled water and 0.5 ml of the dye. 8) Measure the absorbance by spectrophotometer for each one at wavelength 540 nm.

4.6. Analysis calculations

1) 1,5 diphenylcarbazide Weigh .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/.98 = 300 gm/l ml of 98% concentration H2SO4 300/1.833 = 163.66 ml

4.7. 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. 2) Take 7.5 ml of the diluted sample and add 0.4 ml of H 2SO4, 0.5 ml diphenylcarbazide solution and 4.1 distilled water. 3) Prepare a blank by adding 0.4 ml of 3 M H 2SO4 and 0.5 ml of the dye to 11.6 ml of distilled water. 4) Measure the absorbance by the spectrophotometer at wavelength 540 nm.

4.8. Calibration curve

concentration absorbance 0.0003 0.013 0.0015 0.022 0.01 0.254 0.075 0.89 58

4.9. Scanning for iron ions

0 450 475 500 510 520 530 540 550 0 0 0 0 0 0 0 0 0.01 0.17 0.192 0.194 0.195 0.174 0.136 0.09 0.056 0.02 0.149 0.154 0.147 0.146 0.132 0.106 0.071 0.044 0.03 0.23 0.247 0.225 0.242 0.217 0.171 0.107 0.065 0.04 0.287 0.313 0.308 0.307 0.275 0.216 0.142 0.085 0.05 0.334 0.366 0.363 0.363 0.328 0.255 0.168 0.101 0.06 0.442 0.492 0.488 0.491 0.438 0.337 0.229 0.13 0.07 0.529 0.575 0.575 0.58 0.518 0.414 0.305 0.162 0.08 0.603 0.633 0.644 0.659 0.635 0.52 0.409 0.196 0.09 0.666 0.678 0.708 0.725 0.703 0.63 0.487 0.203 0.1 0.709 0.736 0.762 0.778 0.748 0.682 0.588 0.28

59

Conc. calibration Abs.

0 0

0.01 0.195

0.02 0.146

0.03 0.242

0.04 0.307

0.05 0.363

0.06 0.491

0.07 0.58

0.08 0.659

0.09 0.725

0.1 0.778

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5. Results and discussion

5.1. Laminar flow
Time Absorbance 0 0.343 10 0.309 20 0.258 30 0.226 40 0.22 50 0.183 60 0.199 70 0.176 80 0.148

61

5.2. Turbulent flow

Time 0 5 10 15 20 25 30 35 40 Absorbance 0.276 0.227 0.233 0.182 0.18 0.146 0.122 0.117 0.111

62

5.3. For galvanic corrosion with iron

time absorption 0 0 7 0.025 14 0.041 21 0.049 28 0.06 35 0.083 42 0.112 49 0.161 56 0.191

v6 turbulent

v3 laminar

time absorption

0 0.012

5 0.123

10 0.146

15 0.178

20 0.173

25 0.236

30 0.224

35 0.279

40 0.36

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V4 turbulent

time absorption

0 0.013

5 0.06

10 0.113

15 0.129

20 0.154

25 0.169

30 0.2

35 0.256

40 0.314

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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

7. References
1. Yi Huang, Dawei J, Experimental study on seawater-pipeline internal corrosion monitoring system, Sensors and Actuators B 135, pp. 375 380(2008) 2. Grilli R., Baker M. A., Castle J. E., Dunn B., Watts J. F. , Localized corrosion of a 2219 aluminium alloy exposed to a 3.5% NaCl solution, Corrosion Science 52 pp.28552866(2010) 3. Jeffrey R., Melchers R. E., The changing topography of corroding mild steel surfaces in seawater, Corrosion Science ,49, pp. 2270 2288(2007) 4. S. Guang-Ling, Potential and current distributions of one-dimensional galvanic corrosion systems, Corrosion Science 52 pp. 455480(2010) 5. Zumelzu E., Goyos I., Cabezas C., Opitz O., Parada A. , Wear and corrosion behaviour of high-chromium (1430% Cr) cast iron alloys, Journal of Materials Processing Technology 128 pp. 250255(2002).
6.

Osrio W. R., Peixoto L. C., Goulart P. R., Garcia A., Electrochemical corrosion parameters of as-cast AlFe alloys in a NaCl solution, Corrosion Science 52 pp. 29792993 (2010)

66