Corrosion

Corrosion Advanced Module CD-Rom Project
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Corrosion
Corrosion, as we have already learned, is the deterioration of a material (usually a metal) by interaction with its environment. In this module, we are concerned to learn more about the corrosion process, and about some of the ways to prevent corrosion. Our major concern, as with all of CIP is the use of protective coatings. An understanding of corrosion, however, explains many of the ways that coatings function, and sometimes, how they fail.
Copyright NACE International 2003
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Corrosion
Index
Index ..............................................................................2 Corrosion..............................................................................3 Corrosion and Corrosion Rate ..........................................3 Environmental Effects ...................................................4 ISO 12944 part 2.........................................................4 Corrosion of Metals ..........................................................5 Pitting Corrosion............................................................6 Dissimilar Metals ...........................................................8 Summary ........................................................................9 Corrosion Control ................................................................9 Design ...............................................................................9 Inhibitors .........................................................................10 Materials Selection..........................................................11 Cathodic Protection.........................................................13 Protective Coatings .........................................................13 Alteration of the Environment ........................................14 Coating Inspection and Cathodic Protection......................15 Cathodic Protection.........Error! Bookmark not defined. Definition .....................................................................16 How Cathodic Protection Works .................................16 Cathodic Protection Systems ..........................................18 Factors of Cathodic Protection Systems .........................20 Cathodic Disbondment....................................................22 Other Resources for Information .................................23 Dehumidification ............................................................24 Moisture and Humidity ......................................................25 Dewpoint......................................................................26 Effects of Humidity on Corrosion Rate ..........................28 Dehumidification .........................................................29 Refrigeration ...................................................................29 Desiccants .......................................................................30 Benefits of Dehumidification to Coating Applicators ....32 Dehumidification During Post-Application Curing........33 Dehumidification Applications....................................33
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Corrosion
Corrosion is a naturally-occuring phenomenon that results in metal wastage, deterioration of structures, and costs many billions of dollars every year in preventive maintenance or replacement of buildings, structures, machines and equipment.
Corrosion and Corrosion Rate

It has been established that corrosion can occur on steel when the four elements of a corrosion cellanode, cathode, metallic pathway and electrolyteare present. The most common source of electrolyte affecting paints in atmospheric exposure is atmospheric moisture in the form of rain or condensation. Steel temperature changes the corrosion rate in much the same way it affects a typical chemical reaction. Higher temperatures generally create higher corrosion rates. Atmospheric humidity and pollution control the corrosion rate, first by creating an electrolyte, then by affecting the efficiency of the electrolyte. Research shows that steel exposed to high humidity and high levels of atmospheric pollution, such as in an industrial area at a seacoast site, will corrode 15 to 20 times faster than steel exposed in a rural area of high moisture and low pollution. [It should be noted that elevated temperatures (above 100F, 37C) are - in most atmospheric conditions - likely to dry the steel, thereby preventing corrosion] In a rural area the steel may frequently be wet, but the film of relatively clean water produces a low rate of corrosion. In an industrial area, such atmospheric pollution as sulfur dioxide, chlorides, and sulfates cause the water to become acidic, which improves the function of the electrolyte and accelerates the rate of corrosion.
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Environmental Effects
Corrosion rate is influenced by the environment to which the structure is exposed. Various environments have been described in standards such as ISO 12944 part 2, Corrosion Protection of Steel Structures by Protective Paint Systems
ISO 12944 part 2

ISO 12944 has a series of parts that provide information on the principles of corrosion protection work using protective coatings. Part two describes environments as follows: o Atmospheric corrosion o Corrosion in water and soil o Structures immersed in water o Underwater zone o Intermediate (fluctuating level) zone o Splash zone o Structures buried in soil These categories are further defined. For example, atmospheric corrosion is subdivided into 6 categories as follows: o Type C1:very low example heated buildings o Type C2: low example, unheated buildings where condensation may occur o Type C3: medium example, urban and industrial areas, interior of process plants with high humidity and some pollution o Type C4: high example, chemical plants and shipyards
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o Type C5-I: very high (industrial) example, industrial areas with high humidity and aggressive atmosphere o Type C5-M: very high (marine) coastal and offshore areas The type of exposure can be further defined by consideration of climatic conditions ranging from extremely cold to warm and damp, and by a range of special considerations such as the type of water or soil, and chemical or mechanical stresses. The purpose of such detailed descriptions is to guide engineers, consultants and inspectors, to help understand the corrosion that can be expected, and to help select appropriate coatings and working methods.
Corrosion of Metals
All metals may be subject to the same influences that lead to corrosion, and react (to a greater or lesser extent) with the environmental forces that influence activity in corrosion cells. Metals can be ranked according to their natural reactivity in a specific environment. The reactivity of corrosion cells can be measured, and the level of activity of each metal type measured by comparison with a standard electrode such as copper/copper sulfate, silver/silver nitrate, or calomel (mercury) types. The result is generally a table of metals ranked in order of reactivity in a specific exposure. The table below shows some metals, but not all metals, with their relative reactivity in salt water. Notice the presence of Hydrogen, with a nominal voltage of 0.0 volts, used to set a reference point in the table. INSERT TABLE see Munger page 26, table 2.5 The concentration of the electrolyte is influential in determining reactivity, as is temperature. The specific voltage shown in the table relates to the reference electrode used for measurement, and is used here to provide a
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comparison between metals. It can be said, however, that the relative rate of corrosion of a metal in the specific environment is directly related to the test voltage shown here. The more negative voltages indicate a faster rate of corrosion. The rate of corrosion is also affected by the surface chemistry of the metal. The initial rate of corrosion of most metals is generally reduced as the corrosion reaction leads to the formation of salts on the surface, and the metal becomes passivated as a result. The final rate of corrosion may be significantly lower than the initial rate of corrosion for some metals. Stainless steels, for example, may have a significant natural rate of corrosion that is rapidly modified by the formation of a surface layer of salts (oxides) rich in chromium and other metals. The surface layer forms in combination with oxygen, and is less than one micron (0.00004 inches) thick, so is not easily visible. Deprived of an oxygen-rich environment, some grades of stainless steel may corrode very quickly. The chemistry of corrosion is dependent on the environment in which the reaction takes place, and may be difficult to define precisely. The following diagram shows the reaction that takes place on a steel surface in water: Insert Munger page 21, diag. 2.5 This reaction is made more complex by the addition of other chemicals, such as those that might be found in a marine environment (e.g. sodium chloride, etc) or in an industrial environment (e.g. sulfurous, or nitrogenous compounds). Analysis of the products of corrosion may provide many clues about the reaction that created corrosion. This, however, is a subject best left to the metallurgists.
Pitting Corrosion
One form of corrosion that is often seen pitting corrosion - is particularly significant for steel structures. It indicates a
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specific focus of the corrosion reaction, and may lead to significant deterioration in a relatively short (and often unexpected) time. The effects may include: o Penetration of tank shell, with subsequent leaks of the contents into the environment. This may affect ships, railcars, process vessels or many other tank containers. o Penetration of the structure, such as a ships hull o Weakening (often unseen) of structural integrity in load-bearing structures such as bridges. Pitting is generally found when corrosion has become focused on a small area, and most often in acidic environments. The cause may be sludge in the bottom of a tank, part of a structure that has poor drainage, or one of many other, similar reasons. Pitting is a significant factor in corrosion. Metal that has an equal distribution of corrosion across the surface may corrode for many years without serious risk to the structure. Metal that has corrosion pitting may be much more at risk. Inspectors may be required to measure pitting depth in relation to the thickness of original plate. Such measurements are commonly used in ships ballast tanks, or other critical containment structures such as crude oil storage tanks. Both the depth of pitting and a description of the location and distribution are required to fully report the results of inspection testing. Physical measurements can be made using a dedicated pit gauge, or a modified micrometer. Measurements may be made from the good side of the plate using ultrasonic techniques. Other, more sophisticated scanning or mapping techniques may be used, but generally require expensive and complex equipment. Criteria for the depth and/or distribution of allowed pitting must be set by structural engineers.
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Dissimilar Metals
When two different metals are connected together in such a way that an electric current can pass directly from one to the other, the corrosion behavior of both metals changes. Corrosion of the more active metal is generally accelerated, while corrosion of the less active metal is much reduced. This phenomena is used to prevent corrosion when sacrificial anodes are used for cathodic protection (described later) or when zinc pigments are used in primer coatings. When two metals are connected without due design consideration, rapid and unexpected corrosion may occur. Some examples may include: o Steel bolts used to fasten aluminum plates together (aluminum corrodes) o Stainless cladding used to protect insulation materials, and connected to the carbon steel structure (carbon steel corrodes) o Copper pipe connected to cast iron pipe in domestic water supply (cast iron corrodes) In all cases, corrosion would be reduced if the joint between the two metals could be (electrically) insulated.
Cast-Iron & Degraphitization

The corrosion process is often complex. In some alloys, preferential corrosion removes essential metal without any apparent change in structure or surface appearance. An example of this process is cast iron, where the iron elements may be corroded out, leaving the casting with its essential shape, but little of its original strength. Cast iron is more porous than mild steel, allowing electrolyte and other corrosion influences more access to the structures of the alloy. Corrosion dissolves the iron from around the carbon, or graphite, particles, leaving them unsupported in
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the alloy. Weakened by this process, castings are likely to crack or disintegrate under stress with little warning. Other alloys, such as brass, may suffer similar separations because of the corrosion process.
Summary
Corrosion is the result of a complex reaction that may not easily be predicted. An understanding of the basic principles, helps to explain why certain coatings or coating techniques are used. In addition, other corrosion mitigation techniques may be used in conjunction with coatings application. Once again, an understanding of the principles may be useful to achieve best results for effective corrosion prevention.
Corrosion Control
Corrosion can be controlled in a variety of ways, including: o Design o Inhibitors o Materials selection o Cathodic protection o Protective coatings o Alteration of the environment
Design
The way a structure is designed can influence its resistance to corrosion. Generally, structures are less susceptible to corrosion when the design: o Avoids entrapment of moisture, chemical salts, and dirt, and o Allows access for coating operations
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NACE Recommended Practice RPO 178-95 is a valuable guide when designing structures intended for immersion services. The principles of good design are shown, together with suitable treatment that might be used to correct design and fabrication defects prior to coating
Inhibitors
Corrosion inhibitors are substances that, when added to an environment, decrease the rate of attack by that environment. Corrosion inhibitors are commonly added in small amounts to acids, cooling waters, steam, and other environments. They may also be added to water used for water cleaning or water jetting, to prevent flash rusting of the cleaned surface. Inhibitors are also used frequently in oil and gas production. They are introduced into the downhole tubing to isolate the walls of the tubing from salt water and other corrosives in gas, crude oil, and drilling fluids often associated with oil production. Inhibitors may also be used in production tubing, flow lines, and transmission pipelines. Typical inhibitors are based on phosphates, or may be chemical compounds such as1: o Amines, diamines and amido-amines o Some acids, including fatty acids, napthenic acid and sulfonic acid o Petroleum Oxidates Inhibitors are important, however, when added to coatings to create inhibitive primers. The mechanisms of protection against corrosion are similar. Some typical inhibitive pigments include: o Red Lead, lead silico chromate, calcium plumbate
Source Corrosion Engineers Handbook, NACE International
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o Zinc potassium chromate, zinc chromate, calcium chromate Since lead, chromates and other heavy metals are now considered to be hazardous, their use in common coatings has been largely discontinued. They have been replaced with alternative inhibitive pigments such as : o Barium metaborate o Zinc phosphate, calcium phosphosilicate, zinc barium phosphate o Zinc molybdate or by alternative technology, such as the adoption of coating systems that do not contain inhibitive primers, the use of galvanic primers or newer technology such as ionexchange pigments. Inhibitors applied to a surface generally function by passivating the surface, thereby temporarily preventing the chemical reaction that is corrosion. In the case of inhibitive pigments there is often considerable debate about the exact way that corrosion is prevented. In short, the experts do not always agree! A detailed discussion of inhibitors and inhibitive mechanisms per se is outside the scope of this course. (See reference document at end of chapter).
Materials Selection
Some metals, such as gold or titanium, corrode very slowly or not at all, in atmospheric exposure. Other metals corrode at differing and characteristic rates, depending on the exposure conditions. The relative rates of corrosion depend on the corrosion current that is developed when corrosion cells form. For any specific environment the comparative corrosion rates can be shown by a galvanic series. Most commonly, a galvanic series is based on immersion of metals and alloys in seawater, at a standard temperature of 25C (77F)
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In specific immersion environments (e.g. in tanks or vessels) Choosing a corrosion-resistant material can help reduce the rate of corrosion. This slide shows a highly simplified listing of what is sometimes called the galvanic series, a list of materials in order of their corrosion potentials, with the most easily corroded- or most active- at the top, and the least easily corroded- or least active- at the bottom.
Galvanic series of some commercial metals and alloys in seawater (temperature approximately 25C) Magnesium Most Active Zinc Aluminum Mild steel Cast iron Copper Stainless steel-(passive state) Silver Gold Platinum Least Active
Changes in ambient conditions or temperature can affect the order of the galvanic series. By convention, it is said that the more active metals have negative corrosion potentials, and they may sometimes be referred to as anodic. The less active metals may be referred to as cathodic, or noble. General rules of galvanic (dissimilar metal) corrosion are as follows: o When dissimilar metals are connected, the most active (or anodic) metal is more rapidly corroded, while the more noble (or cathodic) metal tends to be protected and corrodes less. o As the potential difference between these two dissimilar metals increases, the rate of galvanic corrosion increases.
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For example, zinc is more active than copper. When zinc is electrically connected to copper, which is relatively inactive, in the presence of a suitable electrolyte, the zinc corrodes more rapidly than its natural rate, and the copper corrodes less rapidly than its natural rate. For any dissimilar metal couple the effect is similar, and the rates of corrosion depend upon the electrical potential difference between the two metals
Cathodic Protection
Cathodic Protection relies on the electrical component of corrosion. Corrosion is defeated by either diverting the corrosion current (through sacrificial anodes) or by opposing the corrosion current. Sacrificial anodes made of relatively active metals, such as aluminum, zinc, or magnesium, are connected to the steel structure to be protected. These anodes then corrode instead of the structural steel. When the sacrificial anode is completely corroded, it must be replaced. An alternate form of cathodic protection (called impressed current) provides an electrical current to oppose the current of the corrosion cell(s).
Protective Coatings
Coatings provide protection to steel by one or a combination of three mechanisms yielding the following three coating types: o Sacrificial coatings, which are rich in zinc. Whenever a scratch or other damage occurs to the zinc and exposes steel, the zinc acts as a sacrificial anode and corrodes to protect the steel surface. o Barrier coatings, which keep moisture away from the steel surface. This removes one of the elements of the corrosion cycle, the electrolyte, thus preventing corrosion. It should be noted that coatings never form perfect barriers, and some penetration by electrolytic liquids is inevitable.
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Coatings in immersion service are particularly likely to absorb moisture, swelling in thickness in the process, and becoming softer, more vulnerable to mechanical damage, and less resistant to electrical (i.e. corrosion) current flow. o Inhibitive coatings, (usually only primers) which in addition to acting as barriers, actively assist in the control of corrosion by using pigments that can provide an inhibitive effect (similar to corrosion inhibitors). Examples include red lead and zinc phosphate. These pigments react with the absorbed moisture in the coating and then react with the steel to passivate it and thus decrease its corrosive characteristics. The protection afforded to steel by protective coatings can be greatly influenced by discontinuities (pores, scratches, pinholes) in the coating film. The rate of corrosion at a discontinuity in a coating film may be affected by a number of factors, including: o Type of coating or coating system o Coating film thickness o Electrolyte presence at the discontinuity o Presence of mill scale on substrate
Changing the Environment

An atmospheric environment may be changed to make it less corrosive. A good example is the use of dehumidification equipment to dry the air in tanks that are being abrasive blasted. By reducing the relative humidity to less than 40% (10% to 15% is possible) corrosion will cease, for all practical purposes. We can hold the blast for many hours or days using this method, preventing flash rusting of the blasted surface.
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When an enclosed space can be sealed, thereby excluding oxygen, corrosion will cease once the prevailing oxygen has been exhausted.
Cathodic Protection
Cathodic protection is a very widely used form of corrosion control. Recall from earlier discussions of corrosion that four things must be present for corrosion to occur: o Anode o Cathode o Electron path (or metallic pathway) o Electrolyte Recall that electrons flow from the anode to the cathode via the metallic pathway, that ions flow from the anode to the cathode through the electrolyte, and that wastage of the metal corrosion - occurs at the anode. Cathodic protection engineers calculate that a current of one amp passing for one year removes 23.5 pounds (10.7kg) of iron through corrosion. Cathodic protection is used to protect structures which are buried, submerged in water, or used to contain liquids that are either primarily water-based (aqueous) or contain water (like an oil storage tank that has some water at the bottom). Cathodic protection depends upon the flow of electric current through the electrolyte, which is whatever the structure is buried or submerged in or what the structure contains. Externally, it is generally fresh water, sea water or wet soil. Internally it is whatever product is carried by the tank or vessel. Cathodic Protection is not an effective way to prevent corrosion in atmospheric exposure Coatings may be applied to structures that are also protected by cathodic protection. The more effectively the coating insulates the structure, the less electric current is required to provide cathodic protection, thereby making the
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system more efficient, reducing both corrosion and the costs of installing and maintaining the system. Definition Cathodic protection may be defined as the reduction or elimination of corrosion by making the structure to be protected cathodic relative to an external anode. The anode may be used to deliver impressed current or may be naturally galvanic (usually magnesium, aluminum, or zinc). Before cathodic protection is applied, corroding structures generally have both cathodic areas and anodic areas (those areas where corrosion is occurring). By application of cathodic protection, all anodic areas can be converted to cathodic areas, the structure becomes cathodic and corrosion will be satisfactorily controlled.
How Cathodic Protection Works

Direct current electricity is associated with the corrosion process on a buried or submerged metallic structure. This is illustrated by the figure below which shows the flow of direct current between anodic and cathodic areas on a section of buried pipe. As shown in this example of a buried structure, direct current is flowing from the anodic areas into the soil, through the soil and onto the cathodic areas, and back through the pipe itself to complete the circuit. For a given driving voltage (the galvanic potential between anode and cathode), the amount of current is limited by such factors as the resistivity of the environment (expressed normally as ohm-centimeters) and the degree of polarization at anodic and cathodic areas. Corrosion occurs where the current discharges from metal into the electrolyte (soil or water) at anodic areas. Where current flows from the environment onto the pipe (cathodic areas), there is no corrosion. Cathodic protection is used to defeat the flow of corrosion current from the discharge point, or anode.
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Cathodic protection by sacrificial anode relies on the natural tendency of current to flow through and then from the most active metal in a metal pairing. Steel surfaces connected to more active metals such as aluminum or zinc automatically become cathodic relative to the other metal. Areas that previously may have been active as anodes on the steel surface become cathodic relative to the more active metal. Corrosion then takes place preferentially on the anode, not on the steel. Cathodic protection of pipe by the impressed current method is illustrated in the diagram below, which shows how the original corroding section of pipe (illustrated above) becomes a cathode by eliminating currentdischarging areas (anodes) on the pipe surface. Cathodic protection current must flow into the environment from a special ground connection (usually called a groundbed) in buried structure applications established for the purpose. By definition, the materials used in the groundbeds are anodes, and material consumption (corrosion) must occur.
A. Original anodic areas discharging current and corroding B. Dotted lines represent lines of current flow which existed prior to applying protection C. Protected structure D. Current flowing from groundbed to surface of protected structure
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Cathodic protection of pipe using sacrificial anodes is equally possible, and does not require a power source to provide the protective current. The anodes would, however, become depleted with time, and replacement may not be easy Cathodic protection systems can be monitored by measuring the electrical potential (voltage) of the protected structure using a reference cell and a special voltmeter. Reference cells are most commonly copper/copper sulfate, silver/silver chloride, or calomel (mercury), but may also be based upon specially refined high-purity zinc.
Cathodic Protection Systems

We will discuss two types of cathodic protection systems: o Galvanic anodes o Impressed current Galvanic Anode Systems The term galvanic often refers to dissimilar metal contact which results in electrolytic potential. An anode is the corroding member in a dissimilar metal combination. A galvanic (also called sacrificial) anode can be described as a metal that has a voltage difference with respect to the corroding structure, is more active than the metal of the structure, and will discharge current that flows through the environment to the structure. Galvanic anodes corrode preferentially to the structure, providing protection. Materials suitable for use as galvanic anodes include aluminum, magnesium, and zinc. Zinc anode bracelets are often used on pipelines submerged in seawater. It should be noted that the pure form of the metal is not effective as anode material because of the tendency to passivate in service. Alloys are made with small quantities of impurities cast in to encourage the free corrosion reaction that is needed for continuing protection.
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Anode materials are cast in numerous weights and shapes to meet cathodic protection design requirements. Data on available anodes can be obtained from suppliers of cathodic protection materials. Impressed Current Systems In an impressed current system, the groundbed anodes are not the source of electrical energy. Instead, an external source of direct current power is connected (or impressed) between the structure to be protected and the groundbed. The anodes then allow the current to discharge to the electrolyte.
The positive terminal of the power source always must be connected to the groundbed, which is then forced to discharge as much cathodic protection current as is desirable. This is important. If a mistake is made and the positive terminal is connected to the structure to be protected, the structure will become an anode instead of a cathode and will corrode actively, which is the opposite of the desired results.
Impressed Current System Anodes

Groundbed anodes, like any metal forced to discharge current, will corrode. It is important to use anode materials that are consumed (i.e. corrode) at relatively low rates and thus permit groundbeds that discharge large amounts of current and still have long service lives. Various materials are used for impressed current anodes: o Scrap steel o Graphite o Iron oxide o High silicon chromium-bearing cast iron o Platinized niobium and titanium The positive terminal of the power source always must be connected to the groundbed. If a mistake is made and the positive terminal is connected to the structure, it (the
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structure) will become an anode instead of a cathode and will corrode
Impressed Current Power Sources

An impressed current system requires a current supply. Common current sources include: o Rectified commercial power o Solar cells o Generators o Fuel cells o Wind-powered cells o Thermoelectric cells Rectifiers are used to convert alternating current from electric utility lines to direct current, and step-down transformers are used to reduce the voltage.
Cathodic Protection Systems

Development of an effective cathodic protection system is a complex task requiring experience, knowledge, and judgment. Some of the factors that must be taken into consideration when cathodic protection systems are designed include: o Regulatory requirements o Economics o Metal to be protected o Service requirements o Total current requirements o Variation in environment o Protective coatings o Electrical shielding
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o Maintenance o Stray current effect o Temperature o Wire and cable o Anode backfill Problem areas include: o Resistance/throw o Cathodic disbondment o Inspection criteria Resistance and Throw Varying resistance in electrolytes (particularly soil) lead to inconsistency in levels of protection provided. Current that provides protection must be calculated to overcome the effects of electrical resistance and provide adequate protection at the surface to be protected. The potential of 0.85V is a minimum requirement for protection. In order for the protected structure to be maintained at this potential (voltage), some areas of it will see an increased (more negative) potential. Due to the size, design, placement of the anodes, and the type and resistance of the electrolyte, this increased (more negative) potential can result in a phenomenon known as cathodic disbondment.
Cathodic Disbondment
Systems operating at a stable potential (voltage) of 0.85V will usually have no detrimental effect upon the coating. However, as the potential is increased (made more negative), reactions take place that can be detrimental to the coating. These reactions result in separation of the coating from the surface, that is, cathodic disbondment. As this potential is increased (made more negative) a slight bit, disbondment generally will occur through hydroxyl (OH) formation. As
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the potential is increased (made more negative), even more disbondment will occur through hydrogen formation.
Cathodic Disbondment Testing

Cathodic disbondment tests are accelerated procedures to determine the comparative degree to which the tested coating may be loosened, or may develop holidays as a result of the action of normal soil potentials or impressed current cathodic protection. ASTM Standard G8 Standard Test Methods for Cathodic Disbonding of Pipeline Coatings describes in detail how cathodic disbondment tests can be performed. Other standards are available, but G8 is probably the most commonly used. Various test methods have been developed and generally include: o Preparation of a sample consisting of the substrate and the applied coating o Creation of an artificial holiday in the coating o Immersion of the sample in a solution of water (preferably distilled): Sodium chloride (NaCl) Sodium sulfate (Na2SO4), or Sodium carbonate (Na2CO3) o The sample is electrically connected to an anode, or, if an impressed current method is used, to a DC voltage source o At specified intervals the specimen is examined for loosening of the coating around the artificial holiday, new holidays, and other required conditions
Inspection Criteria
Detailed criteria for regular inspection of structures that are protected by cathodic protection are defined by both regulations and the governing standards.
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The condition of a pipeline that is protected by cathodic protection may be assessed: o Visually, by walking or flying along the length of the pipeline o Electronically, using survey techniques that inject electrical signals into the line and detect the return signals (e.g. Pearson survey) o Internally, using electronic recording devices (smart pigs) that typically use ultrasonics and other techniques to determine the condition of the pipe. Criteria for successful operation of the CP system include: o Pitting is limited in size and distribution o Cathodic protection voltage levels are adequate at the pipe surface o Groundbed output current is adequate Specific figures for these criteria are generally determined by the owner. Regulations imposed by the US government refer to NACE standards such as that attached to this module to establish the required criteria.
Other Resources for Information

A copy of NACE Standard RP0169-96, Control of External Corrosion on Underground or Submerged Metallic piping Systems, is provided at the end of the chapter as supplemental information on cathodic protection. For anyone further interested in cathodic protection, NACE International offers three general education courses and a certification series: o Cathodic ProtectionAn Introduction o Cathodic ProtectionTheory and Data Interpretation o Cathodic Protection Design I
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o Cathodic Protection Certification courses three levels Some NACE CP courses may also be available for home study.
Dehumidification
This section will focus on dehumidification as a means of controlling the working environment, and describes how dehumidification impedes the corrosion of steel and inhibits flash rusting. Environmental (ambient) conditions, such as humidity and temperature, have a significant impact on surface preparation and coating operations and ultimately on the long-term performance of coatings.
Dehumidification may be defined as The removal of moisture vapor from air to lower its dew point. In normal environmental conditions, coatings must be applied to surfaces within a few hours of cleaning to avoid flash rusting. Coating work often is delayed because of high humidity and/or low temperature. This necessary cycle of blasting and coating on the same day can affect the quality of the coating work. Applicators often hurry to try to beat the weather. Mistakes can add to the overall cost. In many cases, such environmental controls as heating, ventilation, using protective enclosures, lighting, and dehumidification can improve the economics and quality of coatings work. Present-day coatings can reach their maximum protective potential only when applied to a high-quality surface. After proper removal of oil and grease, steel surfaces are usually blasted to remove old coatings, rust, and scale. Coatings must be applied before the surface loses its bright surface appearance and before flash-rusting begins.
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A well-written coating specification requires close monitoring of the surface preparation phase of the coating operation so the full potential of the high-performance coatings may be achieved.
Moisture and Humidity

In normal conditions, all air contains some moisture; the amount it contains depends on the temperature and atmospheric pressure of the air. Generally, pressure is not a significant factor, so only temperature needs to be considered. Relative humidity is the ratio between the actual amount of water vapor in a given volume of air at a definite temperature and the maximum amount that would be present if the air were saturated with water vapor at that same temperature.
RH = amount of water vapor in a given volume of air x 100% maximum amount of water vapor (air is saturated)
Warm air contains or holds more moisture than cold air can hold. The amount of vapor held in the air in summer temperatures may be three times greater than in winter temperatures. When the air contains the maximum amount it can hold at any given temperature, it is said to be saturated. If it contains less, say one-half as much, it is said to be partially (50 percent) saturated, or is said to have a relative humidity of 50 percent. Relative Humidity of air is always in the range of 0 to 100 percent. At zero percent, the air would be perfectly dry; at 100 percent, it is completely saturated. Heating the air does not change its moisture content, which is a quantity of vapor, but it does improve its ability to hold more moisture vapor; and thus, it decreases its relative humidity. Cooling the air reduces the ability to hold moisture vapor and, thus, increases its relative humidity. When air is cooled, its potential saturation is reduced, and the relative humidity without any change in the quantity
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of water present - is increased toward 100% until the air finally becomes totally saturated. When the air is further cooled, the quantity of moisture vapor present exceeds the ability of the air to hold moisture; and the excess moisture vapor, condenses as fog, mist or dew. The most noticeable effect is when the temperature of a surface that is to be coated falls below this critical temperature, and water vapor condenses on the surface. A film of water clearly interferes with the adhesion capabilities of most, if not all, coatings. Metal that is exposed to the atmosphere generally tries to adjust to the ambient temperature, although there may be some delay as temperatures rise and fall through the day. For coating inspectors, the most critical time is generally during the morning, when ambient temperatures may well comply with the requirements, but the metal surface temperature is close to, or below, dewpoint.
Dewpoint Temperature
Whatever the humidity level, it always is possible to cool the air enough to reach saturation and then produce condensation. The critical temperature where the air becomes saturated and capable of producing dew is called the dew point temperature. As relative humidity decreases, water tends to evaporate faster because the air can absorb more of it. As relative humidity increases, water evaporates more slowly. The same is true of most solvents. Most coatings cannot be applied successfully when the relative humidity is very high (generally considered as greater than 90 percent) because of the reduced solvent evaporation rate. This condition can result in solvent entrapment in the applied coating film, together with an impaired cure process, and is likely to cause subsequent coating failure in the form of blistering or other forms of film failure, such as peeling.
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The relationship between relative humidity, temperature, and dew point can be found in tables, or by using a psychrometric chart. The use of the psychrometric chart is illustrated in the example below: The chart shows 70F (21C), 50% relative humidity and a wet bulb temperature of 58.5F (14C). The dew point can be seen to be 50F (10C), which means this air contains the same weight of water vapor as does the saturated air at 50F (10C). By cooling the air from 70F (21C) to 60F (15C), the weight of vapor is not changed, so by definition the dew point is unchanged, i.e., 50F (10C). The relative humidity can be seen to have increased to 73%. Relative humidity and dew point can be calculated by measuring temperatures with direct reading instruments. A practical instrument to use is the sling psychrometer, with which the temperature is measured using wet and dry (thermometer) bulb readings. These measurements can be used to calculate humidity and dew point from psychrometric tables or with special slide rules or calculators. Modern electronic instruments use sophisticated probes and electronics to display many relevant measurements and statistics. In addition, some have a memory and can store many measurements for analysis or downloading to a computer. Like all inspection instruments, the accuracy of gauges should be verified by a calibration process. Visual inspection of thermometers is adequate to ensure the indicating thread is continuous, and comparison with a more accurate version of the same thermometer provides similar results. For electronic instruments, a more sophisticated calibration routine is required, and may involve return to the manufacturer or some other authorized laboratory.
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Calibration kits may be available for individual instruments.
Effects of Humidity on Corrosion Rate

High air humidity can promote rapid corrosion. Normal daytime humidity is typically 50 to 90%, depending on location. Studies show that corrosion is slowed greatly if the humidity is below 60% and virtually ceases below 50%. By holding the relative humidity to a low level (say, below 40%, to allow a safety margin), blast-cleaned surfaces can be held for a long time before coating without of the blast deteriorating. The corrosion rate is governed by the relative humidity of the air in contact with the metal (steel) surface. This can be different from the relative humidity of air only a few millimeters away, especially if the steel surface and the air are at different temperatures. The air next to the steel is called the boundary layer. Unless water is evaporating from or actually condensing on the steel, this air layer will be in moisture equilibrium with the metal surface. In general, it is not practical to measure conditions within the boundary layer, but measurements can be made close to the location by using a sling psychrometer. The temperature of the steel surface can be measured using a contact thermometer. There are two ways to reduce the relative humidity of the boundary layer: o Increase the surface temperature o Reduce moisture content by dehumidification Use of Heat to Increase Surface Temperature The method chosen to increase surface temperature depends on relative cost. With small work pieces, it is possible to heat surfaces using a radiant heater. This method would not be effective for
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large pieces or in a large enclosed area, such as a tank, unless insulation can be provided. Many radiant heaters would be required to combat heat losses from the steel surface to the outside air. Another common technique is to heat the air in order to raise the ambient temperatures, including the steel surface temperature. This can be expensive because heat transfer is poor from air to steel and also, generally, because of the large heat capacity of steel structures. Most of the heat generated is conducted away from the surface that should be heated. The heat source is an important factor. The use of direct heating of any kind may expose heat sources to solvent vapors, resulting in an explosion. The use of gas-burning direct heaters may also be counterproductive. When a gallon of propane is burned, it produces almost 20 gallons (76 litres) of water vapor, achieving exactly the opposite effect than is needed (i.e., less water vapor).
Dehumidification
Previously, dehumidification was defined as the removal of moisture vapor from the air to decrease the dew point temperature. The objective of dehumidification is to reduce the rate of corrosion to minimal levels by reducing the moisture content of the air to a safe level, 50% or less, at the prevailing temperature. A flow of air through the working area always is required, and it is this air that must be dehumidified. The amount of moisture vapor can be reduced by refrigeration or by the use of desiccants.
Refrigeration
Refrigeration is a common and economical method of dehumidification. Ambient air is passed over a series of refrigeration coils. The surface temperature of these coils is set considerably lower than the dew point of the incoming
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ambient air. The air chills, reaches saturation, and deposits moisture as condensation. The condensation is collected and pumped out of the system. The air exits the cooling coil section of the dehumidifier at a reduced temperature, but more importantly with lower humidity. Low temperature air then can be adjusted if necessary, simply by adding (dry) heat to the air stream based on the particular application requirements. This method is advantageous when the air is comparatively warm with high moisture content, and the outlet dew point is above 32F (0C), but is less effective as temperatures and humidity levels decrease in the winter months or in northern climates. In some cases, the cooling coil may freeze, reducing the efficiency of the dehumidifier because the ice deposits insulate the coil. Refrigeration often is used in combination with absorption and adsorption dehumidifiers.
Desiccants
Desiccants are substances that naturally have a high affinity for water, so high they can draw moisture directly from the surrounding environment. Desiccants absorb moisture until they are saturated; then they must be regenerated by a heated air stream or by a chemical process. Most desiccants are solids in their normal state, though there are some liquid desiccants, including: o common sulfuric acid (used in the chemical manufacturing industry), o lithium chloride, or o polymeric materials, such as triethylene glycol. These liquid materials are called absorbent dessicants. Desiccants in solid form are called adsorbent desiccants. Moisture is adsorbed onto the surface of a granular
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material, such as silica gel, which is capable of holding large quantities of moisture. These materials can be dried easily and recycled for further use. For the coating industry, the rotating-bed silica gel adsorbent dehumidifiers are most prevalent. The solid desiccant is contained in a large rotating drum or wheel (10 to 12 revolutions per hour) that contains structured air contact media in the form of a honeycomb. Process air (i.e., the air to be dried and introduced into the area where blasting and coating is taking place), passes through the open flutes in the media and releases its moisture to the silica gel desiccant contained in the media walls. The moist media then rotates into a separate compartment, passing through a hot reactivation (regeneration) air stream, which removes the moisture from the silica gel. The process air and reactivation air streams are separated by a partition. The portion of the honeycomb where the moisture has been removed is exposed again to the process air stream to adsorb more moisture. This is a closed-loop continuous process, and it can operate automatically with little or no manpower required for its operation. Some weak points need to be considered: o If the heat source for the reactivation air stream is interrupted, the wheel continues to operate and the silica gel desiccant becomes saturated. At this point, the unit ceases to function as a dehumidifier. Frequent checks should be made to ensure the reactivation air stream is fully operable. o As a result of the heat reactivation process, the drum (wheel) becomes heated; and this heat energy is transferred to the process air stream and the dehumidified air becomes heated. The normal operating temperature increase is +50F (28C), which means, for 80F (27C) ambient temperature,
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the process air stream outlet air temperature would be about 130F (55C). This additional temperature may create an unacceptable working environment. To solve the problem, a refrigeration chiller must be installed down stream of the dehumidifier, to reduce the temperature to suitable levels. o Large volumes of process air may be moved, so care must be taken to prevent the silica gel from becoming contaminated with dirt, blasting dust, solvent vapors, or oil fumes. Contaminated silica gel cannot adsorb moisture. This protection can be accomplished by the installation and frequent change of filter media on both the process air and reactivation air inlets in the dehumidification unit. Ducting to gather clean air, away from the work operation, may also help to keep the silica gel clean.
Benefits of Dehumidification to Coating Applicators

Contractors can use dehumidification to dry the air in any confined space, such as a tank or vessel, blast the entire surface, clean the surface (i.e. remove the abrasive and dust), and then apply the coatings. Additional benefits include: o Crews can start earlier in the day and work later. o Contamination of previously-applied coatings by the blasting operation can be eliminated. o Overlaps from one coated surface onto another (in the daily blast-then-coat routine) are eliminated. o If more than one coat is applied, then all can be done in ideal conditions. o Extended overcoating intervals can be avoided.
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o Contractor can guarantee, with reasonable accuracy, when the job will be completed. o Dehumidification extends the coating season in some areas by many months. o The contractor can control ambient conditions and not be a victim of weather and atmospheric changes.
Dehumidification during PostApplication Curing

The problem of low solvent evaporation in high humidity environments was mentioned earlier. Dehumidification equipment should be used whenever possible through the curing period to ensure a complete solvent release from the applied coating. Typical solvents used in coatings are heavier than air, and tend to settle to the bottom of a structure, tank, etc., and saturate the air. Once the air at the boundary layer next to the coating becomes saturated, evaporation is retarded or stopped. Solvent then remains in the film during the curing process. The only way to prevent this situation is with constant ventilation of the solvent-laden air during the coating operations. If the make-up air is already at 85% relative humidity or greater, solvent evaporation will not improve or may be retarded. Ideally, the make-up air should be dehumidified air to enhance the amount of solvent, which can be removed per cubic foot of make-up air. The more air which can be dried (50 % relative humidity, or less), the more solvent can be evaporated from the applied coating with the same volume of ventilation air. Post-application ventilation and dehumidification processes should be routinely monitored by the inspector and all relevant parameters recorded in the daily records.
Dehumidification Applications
Dehumidification equipment commonly is used in the coatings industry for tank lining projects in adverse weather conditions. The ambient atmosphere in the tank can be
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controlled throughout the project. It is not uncommon to allow blast-cleaned steel to stand for days, or even weeks before coating, provided low relative humidity can be maintained. Prudent applicators keep a standby dehumidifier on site. Equipment failure may result in the loss of days of surface preparation work, particularly if the equipment fails at night and the problem is not found until the following day. Buried tanks are particularly appropriate for the dehumidification process because of the high-insulation factor of the surrounding earth. Blasting and painting ships ballast tanks or cargo tanks are other common applications. Dehumidification equipment can be helpful in tropical climates throughout the year, provided it is sufficiently powerful to cope with sometimes extremely high temperatures and moisture levels. Further information on this subject can be found in NACE Technical Report 6A192, Dehumidification and Temperature Control During Surface Preparation, Application, and Curing for Coatings/Linings of Steel Tanks, Vessels, and other Enclosed Areas

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Corrosion Advanced Module CD-Rom Project

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Corrosion and Corrosion Rate

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ISO 12944 part 2

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Cast-Iron & Degraphitization

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Source Corrosion Engineers Handbook, NACE International

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Changing the Environment

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How Cathodic Protection Works

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Cathodic Protection Systems

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Impressed Current System Anodes

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structure) will become an anode instead of a cathode and will corrode

Impressed Current Power Sources

Cathodic Protection Systems

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Cathodic Disbondment Testing

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Moisture and Humidity

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Calibration kits may be available for individual instruments.

Effects of Humidity on Corrosion Rate

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