Water Corrosivity A major use of water in industry is the transfer of heat and the production of steam.
There is extensive use of cooling water in almost every manufacturing process, in commercial air conditioning, and even a substantial percentage in domestic air conditioning. Water is used in the passive sense for potable and for fire control purposes. Fossil and nuclear fuel steam plants are encountered in the heating and power generating fields. According to the American Waterworks Association (AWWA) industry database, there is approximately 1,483,000 km of municipal water piping in the United States. This number is not exact, since most water utilities do not have complete records of their piping system. The sewer system consists of approximately 16,400 publicly owned treatment facilities releasing some 155 million meter cube of wastewater per day (1995). The total annual direct cost of corrosion for the nation’s drinking water and sewer systems was estimated at $36.0 billion. This cost was contributed to by the cost of replacing aging infrastructure, the cost of unaccounted-for water through leaks, the cost of corrosion inhibitors, the cost of internal mortar linings, and the cost of external coatings and cathodic protection. Water can be corrosive to most metals. Pure water, without dissolved gases (e.g., oxygen, carbon dioxide, and sulfur dioxide) does not cause undue corrosion attack on most metals and alloys at temperatures up to at least the boiling point of water. Even at temperatures of about 450oC, almost all of the common structural metals, except magnesium and aluminum, possess adequate corrosion resistance to high-purity water and steam. In summary, the factors influencing the corrosion of materials in water systems are:
1. Physical configuration of the system; 2. Chemistry of the water (hardness salts, chlorides, and dissolved gases being the most 3. 4. 5. 6.
important); Presence of solids in the water; Flow rate; Temperature of the water; Presence of bacteria. Corrosion Cells and Factors Causing Corrosion Introduction As described in the previous Chapter, corrosion damage may take various forms which are themselves triggered by apparently different compounding factors. The initiation and
of temperature. by which differences in potential may develop on metal surfaces . Mears and Brown have summarized 18 mechanisms. steady or cyclic) Oxide scales (continuous or broken) Presence of deposits on surfaces Fayed surfaces and the possibility of corrosion crevices Galvanic effects between dissimilar metals Occasional presence of stray electrical currents from external sources The nature of the driving forces behind these factors has been the subject of scientific studies by many scientists in the early part of the twentieth century.progression of corrosion processes indeed depend on the complex interaction of a multitude of factors such as:
• • • • •
• • • • • •
Nature of the metal or alloy Presence of inclusions or other foreign matter at the surface Homogeneity of the metallic structure Nature of the corrosive environment Incidental environmental factors such as variations in the presence of dissolved oxygen. and in the velocity of movement either of the environment or of the system itself Other factors such as stress (residual or applied. Causes of corrosion currents
. listed in the following Table. In a landmark paper.
Clearly. X-ray diffraction and surface analysis are specialized tools used in such investigations. hardness testing. The large segment of the paint industry committed to the manufacture and application of products for the protection of metals. insufficient repairs due to short term profit motives. agricultural machinery. In contrast to the traditional scientific mechanistic approach. as well as the large-scale operations of the galvanizing industry attest to the importance of controlling atmospheric corrosion. fractography. It is thus apparent that there can be multiple causes associated with a single corrosion mechanism. for instance. inadequate training and poor communication. metallography. buildings and outdoor monuments. These failure investigations are typically carried out in a detailed mechanistic ‘bottom-up’ manner whereby a failed component would be sent to the laboratory where analytical techniques would then be used following well established protocols. (reference) Economic losses caused by atmospheric corrosion are tremendous and therefore account for the disappearance of a significant portion of metal produced. Consider. this approach alone provides little or no insight into the real causes of failure. a poor organizational ‘safety culture’. Chemical analysis. fences. exposed metals on buildings. automobile
.This is consistent with the lessons to be learned from the UK Hoar Report which stated that corrosion control of even small components could result in major cost savings because of the effect on systems rather than just the components Atmospheric Corrosion Introduction Atmospheric corrosion is surely the most visible of all corrosion processes. defective supplier's products. rusty bridges. optical and electron microscopy. or an incorrect material selection. Underlying causes of serious corrosion damage that can often be cited include human factors such as lack of corrosion awareness. flag poles.g.Establishing the real causes of corrosion failures (often related to human behavior) is a much harder task than merely identifying the failure mechanisms.There is a vast body of information relating practically all the previously listed factors to actual field observations and subsequent analysis of failed components. However. e. steel structures.Further underlying causes may include weak maintenance management systems. systems engineers prefer the ‘top-down’ approach that broadens the definition of the system and is more likely to include causes of corrosion failures such as human behavior. a comprehensive failure investigation providing information on the root cause of failure is much more valuable than one merely establishing the corrosion mechanism(s).
Since the corroding metal is not bathed in large quantities of electrolyte. most atmospheric corrosion operates in highly localized corrosion cells.300 m. calculation of the electrode potentials on the basis of ion concentration.mufflers or bodies. Furthermore. atmosphere. and nitrogen oxides (NOx). Sulfur dioxide from burning coal or other fossil fuels is picked up by moisture on dust particles as sulfurous acid. This is oxidized by some catalytic process on the dust particles to sulfuric acid which settles in microscopic droplets and fall as acid rain on exposed surfaces. particularly where corrosive pollutants are present. sometimes producing patterns difficult to explain as in the example of this rusting galvanized roof. acid film on exposed surfaces. most environments are mixed and present no clear demarcation. since the Aloha incident in 1988. These are usually various forms of chloride which may be
. The result is that contaminants in an industrial. However. all of the electrochemical factors which are significant in corrosion processes do operate in the atmosphere. Atmospheric corrosion has been reported to account for more failures in terms of cost and tonnage than any other type of material degradation processes. the type of atmosphere may vary with the wind pattern. These constitute direct losses from corrosion. particularly by the aircraft industry. and other electrochemical operations are not as simple in atmospheric corrosion as they are in liquid immersion corrosion. a precursor to acid rain.
Rusting galvanized roof with regular bands of rust Thus. Types of Corrosive Atmosphere
While atmospheres can be classified into four basic types. the backbone of smog in modern cities. produce a highly corrosive.
All of the general types of corrosion attack occur in the atmosphere. plus dew or fog. other corrosive pollutants may be present. when a Boeing 737 lost a major portion of the upper fuselage in full flight at 7. the determination of polarization characteristics. This particular type of material degradation has recently received more attention. In addition to the normal industrial atmosphere in or near chemical plants. and the myriad of other metal items which are discarded when they become unusable as a result of corrosion. or with local conditions such as illustrated in the following. wet.
Industrial An industrial atmosphere is characterized by pollution composed mainly of sulfur compounds such as sulfur dioxide (SO2).
In the Tropics. (courtesy Major S. similar to what is experienced on a regular basis by sea patrolling aircraft or helicopters as shown in the following Figure. Pacific Corrosion Control Corporation) Rural Rural atmospheres are typically the most benign and do not contain strong chemical contaminants. The quantity of salt deposited can vary greatly with wind velocity and it may. and is greatly affected by wind currents. In sheltered areas.
Sea salt deposited on the external surface a) of a Cormorant sea and rescue helicopter radar antenna.much more corrosive than the acid sulfates. even form a very corrosive salt crust. and b) salt causing corrosion to the antenna internal components due to a broken seal.J.R. the daily cycle includes a high relative humidity. However. Arid or tropical atmospheres are special variations of the rural atmosphere. In arid climates there is little or no rainfall. in addition to the high average temperature. some combinations of conditions may actually cause relatively severe corrosion problems. Giguère)
The quantity of salt contamination decreases with distance from the ocean. intense sunlight. The marine atmosphere also includes the space above the sea surfaces where splashing and heavy sea spray are encountered. Marine
A marine atmosphere is laden with fine particles of sea mist carried by the wind to settle on exposed surfaces as salt crystals. and long periods of condensation during the night. This situation is encountered along the desert coast of northern Africa. that is unless one is close to a farm operation where byproducts made of various waste materials can be extremely corrosive to most construction materials.
Aircraft carrier top deck. (courtesy Mike Dahlager. The reactivity of acid chlorides with most metals is more pronounced than that of other pollutants such as phosphates and nitrates.
. in extreme weather conditions. the wetness from condensation may persist long after sunrise. but there may be a high relative humidity and occasional condensation. Indoor Normal indoor atmospheres are generally considered to be quite mild when ambient humidity and other corrosive components are under control. Such conditions may produce a highly corrosive environment. The equipment exposed to these splash zones are indeed subjected to the worst conditions of intermittent immersion with wet and dry cycling of the corrosive agent as illustrated in the following Figure.
There will be a flow of electrons from certain areas of a metal surface to other areas through an environment capable of conducting ions. the wires coming to the box were buried without additional insulation and in constant contact with much cooler ground than ambient air in the room. Evans. the constant condensation on a cold metallic surface may cause an environment similar to constant immersion for which a component may not have been chosen or prepared for. [which] may be defined as destruction by electrochemical or chemical agencies. While the junction box in this example was only at the ground level. below ground where high humidity may prevail. Ulick R. Such systems are commonly encountered in confined areas close to ground level or.. any enclosed space which is not evacuated or filled with a liquid can be considered an indoor atmosphere. Even in the absence of any other corrosive agent. Corrosion Electrochemistry Introduction While corrosion can take any one of the several forms. which in the presence of condensation or high humidity could prove to be highly corrosive. the mechanism of attack in aqueous environments will involve some aspect of electrochemistry. such an environment may contain fumes. In this context. If not ventilated.While there is no typical contaminant or set of conditions associated with an indoor atmosphere. has said that "Corrosion is largely an electrochemical phenomenon. It results from the overwhelming tendency of metals to react electrochemically with oxygen. and other substances in the aqueous environment. Historical Theories on Corrosion by UR Evans Corrosion in an aqueous environment and in an atmospheric environment is an electrochemical process because corrosion involves the transfer of electrons between a metal surface and an aqueous electrolyte solution. the term anode is used to describe that portion of the metal surface that is actually corroding while the term cathode is used to describe the metal surface that consumes the electrons produced by the corrosion reaction.". The following Figure shows the advanced corrosion of the frame and contacts in an electric junction box only four years after a building was completed. worse. water. the British scientist who is considered by many as the "Father of Corrosion Science". (reference)
During such a reaction. it is important to understand the basic nature of electrochemical reactions. electrons are transferred. The fact that corrosion consists of at least one oxidation and one reduction reaction is not always as obvious as it is in batteries. or. a piece of zinc immersed in hydrochloric acid solution is undergoing corrosion. Since metallic corrosion is almost always an electrochemical process. The two reactions are often combined on a single piece of metal as illustrated schematically here for a piece of steel and in the following Figure for a piece of zinc immersed in an acidic solution. This reaction produces electrons and these pass through the solid conducting metal to other sites on the metal surface where hydrogen ions are reduced to hydrogen gas according to equation. in fact. It is also a chemical reaction which involves oxidation and reduction. viewing it another way. according to equation. The Daniell cell was the first truly practical and reliable electric battery that supported many nineteenth century electrical innovations such as the telegraph.
Electrochemical reactions occurring during the corrosion of zinc in air-free hydrochloric acid In this Figure. an oxidation process occurs together with a reduction process. The discoveries that gradually evolved in modern corrosion science have. These principles are illustrated with the use of a Daniell cell in which copper and zinc metals are immersed in solutions of their respective sulfates. played an important role in the development of a multitude of technologies we are enjoying today.
These equations illustrate the nature of an electrochemical reaction for zinc. zinc is transformed to zinc ions. The overall corrosion processes are summarized in the following equation:
.An electrochemical reaction is defined as a chemical reaction involving the transfer of electrons. At some point on the surface.
St. reversible. for corrosion to occur there must be a formation of ions and release of electrons at an anodic surface where oxidation or deterioration of the metal occurs. ?
. other research partners in the European Commission. or the formation of negative ions.Briefly then. An international team of researchers is hopeful that corrosion inhibitors and surface treatments will help to prolong the life of these irreplaceable instruments.funded ?Corrosion of Lead and Lead-Tin Alloys of Organ Pipes in Europe? (COLLAPSE) project include the Göteborg University?s Göteborg Organ Art Center (GOArt) (Göteborg. and the organ manufacturer Marcussen & Søn Orgelbyggeri A/S (Aabenraa. Often constructed of lead or lead-tin alloys. Staff Writer An important part of Europe?s rich musical heritage is crumbling away? literally.? ?The ideal protection treatment should be easy to apply by restorers. Chalmers University of Technology (Göteborg. Sweden). ?The treatments hitherto used for corroded pipes have been irreversible. and its original characteristics. even worse. irreplaceable historic pipes have been exchanged for new ones. There are more than 10. ?New materials with different compositions and behaviors have been used to repair damaged pipes?sometimes with destructive results. the pipes on organs at churches and other venues throughout Europe are under attack from corrosion. and some were built more than 500 years ago.? says Martini. thereby causing damage to the instrument as a whole. ?We are not developing a new inhibitor.000 historical pipe organs in Europe.? says Carla Martini. The anodic and cathodic reactions must go on at the same time and at equivalent rates. Sweden). There must be a simultaneous acceptance at the cathodic surface of the electrons generated at the anode. and should not change too much the color of the metal or?most important?the sound of the pipe. Research Associate with the University of Bologna?s Institute of Metallurgy (Bologna. Italy). The foot is the conical tip of the pipe that is close to the wind inlet. its quality of sound. corrosion occurs only at the areas that serve as anodes. Veazey. Jakobi Church (Lübeck. However. This acceptance of electrons can take the form of neutralization of positive hydrogen ions.? Aside from the University of Bologna. by Matthew V. Germany). Martini points out that corrosion most often concentrates around the foot of an organ pipe. Denmark). costeffective. but we are trying to apply known inhibitors and/or treatments to [lead or lead-tin pipes]. Or.
the prospect pipes? visible from the outside?are more tinrich compared to the pipes inside the organ. In general. All field studies will concentrate on high-lead organ pipes?pipes with a tin content of less than 2
. which has pure lead pipes and was built in 1467. The Chalmers investigators are analyzing the environments of the church and the organ wind supply. finally. It is very serious if the corrosion reaches the mouth area because the historical sound quality will be lost and the sounding cultural heritage is forever gone. ?If nothing is done. Research Engineer with GOArt. and particularly the metal. and their colleagues are studying various other ?reference organs? in several countries as well. and surface structures.? he says.? Bergsten says that older pipes generally have a higher lead content. Martini. high-tin alloys or pure tin are used for pipes in the facade of the organ. from country to country and from organbuilder to organbuilder. but he adds that materials selection also was influenced by regional traditions as well as the price and availability of tin.? she says. The sound is generated in the mouth area. Researchers from GOArt are documenting pipe corrosion damage with descriptions and photographs. there will be cracks and. Tin makes the pipe look brighter and shinier. Bergsten. ?Tin was also much more expensive than lead.? adds Carl Johan Bergsten. Martini points out that the pipes in a single organ may have very different compositions. represented a major part of the cost for an organ in older times [today the cost of labor is the most expensive part]. However. edges. ?The material. Jakobi Church?s noteworthy Stellwagen organ. The pipe will be silent because the wind will not flow through the pipe mouth area but will disappear through the holes. In each country. their roles in the field studies are unique. ?The content of tin in lead alloys used for pipes may vary in a wide range. ?In Italian organbuilding. and the tone quality is extremely sensitive to changes in the mouth area geometries.? The COLLAPSE project involves many variables from a metallurgical standpoint. they are examining one corroded instrument and one that is not significantly affected by corrosion.It?s worth noting that this kind of corrosion typically affects the inner side of the pipe and may not be visible from the outside until the pipe breaks out. In fact. whereas pipes behind the facade are mostly made of high-lead alloys. University of Bologna team members are responsible for taking samples from corroded pipes so that they can identify phase composition and morphology of corrosion products as well as characterize the material. ?The corrosion starts in the lower part of the foot and moves gradually upward in the pipe toward the mouth area. holes in the pipe foot wall.? she says.? The research began with an investigation of St.
especially oak [common in organs].? Bergsten points out that high concentrations of acetic acid (CH3COOH)? from 200 to 2.? says Martini. ?There are also preliminary results showing that the tin concentration in the alloy is important for the pipe metal corrosion resistance.wt%?that appear to be affected by organic acids in the indoor environment.? Bergsten points out that the most promising conservation strategy at this point is changing the corrosive environment and cleaning the corroded pipe metal surface with various products and methods. Bergsten cautions that it is too early to definitively explain why the organ pipes are corroding.? Despite the COLLAPSE team?s findings to date.? he says. ?The objective is therefore to remove corrosive compounds? salts?from the surface. humidity. is known to emit organic acids.5 wt% tin. ?In addition. ?As to the material. Bergsten predicts that the team will need to resort to some type of surface coating.000 ppb?have been measured in the organ wind. ?Cleaning the corroded pipe is done primarily to decrease the rate of corrosion. ?We suspect that a high concentration of organic acids in the organ environment is a key factor in influencing corrosion. according to the measurements made by the Department of Environmental Inorganic Chemistry at Chalmers University of Technology. and corrosive emissions from materials inside and outside the organ.? If this approach is not successful. condensation phenomena inside the pipe. The insoluble corrosion products?for instance.? he says. ?Wood. lead white?are not to be removed. Martini notes that organbuilders that build new organs still use these alloys to produce pipes.
. sulfur dioxide [SO2] and nitrogen dioxide [NO2]?do not seem to be the major causes for the corrosion of organ pipes. formic acid [HCOOH] and aldehydes were detected. we can say that the extent to which ancient samples are affected by corrosion decreases with increasing tin content in the alloy?in the range of 0 to 1. Also. ?We have found corrosive factors at the reference organs [but] it is important to also investigate other possible corrosive factors like temperature.? he says. Cleaning should not affect the metal itself. Inorganic air pollutants? for instance. combinations of the different possible corrosive factors above could be the reason for the corrosion. Laboratory research at Chalmers has shown that acetic acid in low concentrations is corrosive to lead.