NORTON CORROSION LIMITED

CORROSION CONTROL TRAINING COURSE

CORROSION CONTROL SPECIALISTS SINCE 1959

1-800-426-3111

Phone: 425-483-1616 Fax: 425-485-1754

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CORROSION CONTROL TRAINING COURSE TABLE OF CONTENTS

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INTRODUCTION .........................................................................1 CORROSION FUNDAMENTALS ................................................1 Corrosion Cell Galvanic Series Chemical Activity Physical Relationship Corrosion Types AFFECTED STRUCTURES ........................................................5 Loading Docks Product Piping Storage Tanks Reinforced Concrete CORROSION CONTROL ..........................................................11 Material Selection Environmental Coatings Cathodic Protection CATHODIC PROTECTION .......................................................13 Sacrificial (Galvanic) Impressed Current Design Details Criteria for Protection Installation

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INTRODUCTION

Corrosion can be defined as the deterioration of metal due to its interaction with the environment. Corrosion is a natural phenomenon, which should not surprise one but rather should be expected to occur. Metals are high energy materials, which exist because heat energy was added to natural iron ores during the smelting process. Nature by environmental contact constantly attacks these high energy materials and breaks them down to the natural elements from which they were derived. Corrosion is a very costly process resulting both in product loss and environmental deterioration. In more familiar terms, corrosion often results in lost business and has been responsible for injury and even death.

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CORROSION FUNDAMENTALS

Corrosion is an electrochemical process occurring at the interface between metal and environment. It is not a constant process and is highly complex. However, certain conditions must be present before that corrosion mechanism is initiated. Those conditions include the following: 1. Two areas on a structure or two structures must differ in electrical potential. Those areas called anodes and cathodes must be electrically interconnected. Those areas must be exposed to a common electrolyte (soil or water).

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When these conditions exist, a corrosion cell is formed in which the cathode remains passive while the anode deteriorates by corrosion. As a result of this process, electric current flows through the interconnection between cathode and anode. The cathode area is protected from corrosion damage at the expense of metal, which is consumed at the anode. The amount of metal lost is directly proportional to the DC current flow. Mild steel is lost at approximately 20 pounds for each ampere flowing for a year. Cast iron is less active and lead is much more active with losses of nearly 75 pounds per ampere per year. The amount of corrosion current that flows and thus the possibility for damage are functions of several variables including potential difference between anode and cathode, circuit resistance, chemical activity of the environment and several physical relationships. With all else remaining the same, a larger potential difference produces more corrosion damage. All metals possess an intrinsic activity, which represents the natural vigor with which the metal will interact with the environment. Several common metals are listed in Table 1 by activity ranging from active to passive. This listing is defined as a galvanic series and is based upon typical oxygenated seawater as the electrolyte.

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Table 1 TYPICAL GALVANIC SERIES METAL Commercially Pure Magnesium Magnesium Alloy Zinc Aluminum Alloy Commercially Pure Aluminum Mild Steel (clean & shiny) Mild Steel (rusted) Cast Iron (not graphitized) Lead Mild Steel in Concrete Copper, Brass, Bronze High Silicon Cast Iron Carbon, Graphite, Coke VOLTS (CSE) -1.75 -1.60 -1.10 -1.05 -0.80 -0.50 to -0.80 -0.20 to -0.50 -0.50 -0.50 -0.20 -0.20 -0.20 +0.30

Interconnecting any two of those metals in an electrolyte will create a corrosion cell proportional in strength to the separation on the table. For example connecting zinc with carbon will produce a corrosion cell with a potential of about 1.4 volts. Zinc is the active element or the anode and carbon is the passive element or the cathode. The interconnecting wire will conduct electronic current and corrosion will occur at the zinc anode. This damaging corrosion cell becomes a beneficial cell when properly constructed and is used every day as a dry cell battery. Corrosion is harnessed to provide a source of electric current as illustrated in Figure 1.

Figure 1

Circuit resistance also impacts the activity of a corrosion cell but in an inverse manner. Increased circuit resistance decreases the activity of the cell and less corrosion then occurs. Circuit resistance includes the metallic connection between anode and cathode as well as the

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interface resistance between electrode and environment and the resistance of the environment (Figures 2 and 3). Increasing any of these resistances reduces the corrosion activity.

Figure 2

Figure 3

Chemical activity of the environment directly affects corrosion rate. A passive environment is one with high pH, low moisture content, lack of salts available to enter into solution and low electrical conductivity (high resistivity). Corrosion cell activity is enhanced when the environment is heterogeneous even if a portion of the exposure is to a passive environment. Increased temperature results in increased chemical activity and increased corrosion since kinetic energy rises, viscosity is reduced and solubility generally increases with temperature. Resistivity is a measure of the natural resistance an environment provides to corrosion activity. Resistivity is one environmental factor, which can be easily monitored to predict corrosivity. Several factors must be considered when determining the compatibility of metal exposed to a particular environment but the following table serves as a guide in predicting the corrosivity of soil with respect to resistivity alone.

CLASSIFICATION Low Resistance Medium High Very High

ELECTROLYTE RESISTIVITY (ohm-cm) 0 2,000 10,000 Above to to to 2,000 10,000 30,000 30,000

ANTICIPATED CORROSIVITY Severe Moderate Mild Increasingly Less

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Physical relationships affecting corrosion activity include stress, erosion and exposure limits. Stresses are created by cold working which impact local areas only. The stressed areas become much more active relative to adjacent unstressed areas and corrosion damages the former. Erosion affects corrosion by physically removing rust or corrosion products in local areas exposing clean metal to the environment (Figure 4) which is then damaged by further corrosion.

Figure 4

Those corrosion products were acting as a natural coating before erosion damaged that coating resulting in larger areas exposed to future corrosion. Exposure limits provide a similar scenario where a coated metal is protected from corrosion until coating damage occurs as illustrated in Figure 5.

Figure 5

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Corrosion is then concentrated at the small exposed area and rapidly extends into the metal. Coating adjacent to the defect is quickly compromised when corrosion damages substrate metal and undercuts nearby coating. An uncoated structure can often times be preferable to a poorly coated structure. An uncoated structure in the same environment would expose a larger surface area to corrosion and losses would be distributed across the entire surface with penetration being greatly reduced. Different corrosion types will occur depending on the physical and metallurgical nature of the metal, and the prevailing environmental conditions. Some of these types are listed below.

CORROSION TYPE Uniform or near uniform Localized

CHARACTERISTIC Corrosion attacks all areas of the metal at the same or similar rate. Some areas of the metal corrode at different rates due to heterogeneities in the metal or environment. This type of attack can approach pitting. Very highly localized attack resulting in small pits that may penetrate to perforation.

Pitting

Many metal structures can continue to perform their design function while experiencing limited corrosion rates, particularly when corrosion is uniform. However, when the structure functions as a vessel, localized and pitting corrosion usually result in rapid failure. Some structures can continue functioning even after corrosion has penetrated the full cross section such as foundation piles.

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AFFECTED STRUCTURES

Loading Docks Loading docks are quite susceptible to corrosion damage by the exposure to heterogeneous environments. Steel piling often extend 50 to 100 feet in length from pile cap to tip. The corrosion environment may range from highly oxygenated saltwater in the splash zone to nonconductive bedrock with several variations between. Freshwater intrusion will often overflow the higher density saltwater creating highly active corrosion layers. Piles may be provided with protective coating of varying integrity and normally restricted to the water zone. Piles are frequently bonded together creating a common structure several hundred feet in length. Propwash, wave action and tidal fluctuations constantly affect the piles at one elevation resulting in significant corrosion zones by depth (Figure 6).

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Figure 6

Electrical interference can have profound corrosion affects on loading docks when corrosion currents are discharged from the piles into the water. The currents can result from DC operations both onboard ships and the dock (cathodic protection systems, welding, DC crane motors). A cathodically protected dock can be impacted by large ships without cathodic protection in metallic contact with the dock, pipelines from shore facilities without protection in contact with the dock and even improperly operated cathodic protection systems. Product Piping Product piping is susceptible to corrosion because it spans long distances through different soil types, it may be coated with materials and quality of differing integrity, it may be interconnected to more noble materials through grounding or incidental contact and it may be located in close proximity to foreign cathodic protection or to high power lines where stray current interference may cause corrosion damage. Well coated piping is expected to be installed with select granular backfill to protect the coating from physical damage. The piping is normally electrically isolated from foreign piping, service lines and transmission piping using insulating flange kits, insulating unions or dresser couplings. Contact with casings and above grade pipe racks is normally prevented by utilizing electrically insulating spacers. Any compromise of that isolation or coating can initiate corrosion and render existing cathodic protection ineffective. Storage Tanks Underground storage tanks (USTs) are more susceptible to corrosion damage than a typical isolated buried structure. Most USTs are electrically connected to other buried structures through their electrical pumping systems and inadvertent contact with adjacent utilities usually at the product or vent piping (Figure 7).

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Figure 7

The typical storage tank often penetrates more than 10 feet below grade, which is commonly below the water table during wet periods. The large surface area of the storage tank brings it into contact with many different soil strata. Uncoated piping is commonly interconnected to a coated tank with questionable coating integrity. Tanks are often installed in close proximity to rights-of-way, which contain cathodically protected gas or water piping with the potential for damaging direct current interference. Buried storage tanks can also be frequently subject to installation abuses as illustrated in Figures 8 and 9.

Figure 8

Figure 9

Aboveground storage tanks (ASTs) are frequently damaged by corrosion due to contact with corrosive soil and exposure to moisture. A typical AST can have 10,000-30,000 ft of steel

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exposed to corrosive soil and the bottom plates are not coated. The large plates are welded together creating heterogeneous metallurgy and stresses, which are capable of initiating damaging corrosion cells. Some ASTs are constructed over concrete ringwalls for foundation support. That exposes steel plates to typically passive concrete and potentially active soil located inside the ringwall. Dikes surrounding ASTs to contain spilled product can also trap water from rainfall and snow melt which tends to activate drier soils and support corrosion on the tank floor. ASTs used for fuels are required to be grounded which creates the active galvanic couple between the steel plates and the passive copper grounding. The steel becomes the anode and corrosion damage near the ground connection can be expected. Reinforced Concrete Reinforcing steel is generally very compatible with concrete because both have similar thermal expansion properties and concrete normally provides excellent corrosion protection for underlying steel. Concrete is a good electrolyte similar to soil since it is highly porous and usually contains lots of water in that pore space when exposed to weather or soil. The natural corrosion protection of reinforcing steel is the result of the highly alkaline portland cement which allows a stable, protective oxide film to form on the surface of the steel (Figure 10).

Figure 10

The surface of the steel is protected from corrosion by this passivating film while the alkalinity is uniformly maintained. However, corrosion of reinforcing steel will occur when the film is weakened or damaged in the presence of moisture and atmospheric oxygen. The protective film will be destroyed by any of the following: 1. 2. Concrete not fully encasing the steel. Concrete alkalinity lost by reaction with aggressive gases.

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Concrete contaminated by excessive amounts of chloride or other aggressive ions.

If one or more of these conditions coexist with moisture and oxygen at the steel-toconcrete interface, corrosion can occur. Moisture is present in nearly all concrete structures and atmospheric oxygen is present unless the structure is deeply submerged. The depth of concrete cover over rebar and the quality of the concrete also play a role in determining the length of time required for chlorides to diffuse through the concrete and reach the surface of the steel. Concrete quality is known to be adversely affected by exposure to levels of sulfates as low as 150 parts per million (ppm). The beneficial alkalinity of concrete is lost by exposure to carbon dioxide from air or water. The result is a decrease in concrete pH from the more typical value of 12 to a value of about 8 where steel becomes active toward corrosion. Chlorides originating from deicing salts dropped on the roadway from salt laden marine air or even chlorine gases from a swimming pool quickly gain entry into the top layer of concrete through the concrete pore space. The chlorides then migrate through the concrete and once reaching the surface of the reinforcement cause small areas of the steel surface to become active anodes as the protective oxide film is destroyed (Figure 11).

Figure 11

In this corrosion cell, the anode to cathode ratio is extremely small and very rapid metal loss occurs at the anodic area. Because the corrosion product is several times more voluminous than that of the substrate steel, huge mechanical tensile stresses are created which eventually destroy the bond between the concrete and the reinforcement. The end result is a delaminated or spalled area of concrete (Figure 12).

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Figure 12

This damage actually accelerates the corrosion rate at the anodic areas near the edge of the spall because the additional oxygen and moisture available in the damaged area tend to increase the driving potential of the corrosion cell. The delaminated area eventually spreads until an entire section of concrete is destroyed. This exposes the reinforcing steel to more generalized corrosion because it then becomes exposed to the elements without the overall passivating effect of the concrete. There is very little loss in cross section or overall metal volume of the reinforcing steel in the mechanism described above. The majority of the steel surface remaining in the concrete is passivated so the corrosion damage is concentrated at local areas where chlorides have destroyed the passivating film. Large metal losses in cross section do not occur until the reinforcing bar is directly exposed to the elements. Therefore, the loss of strength in the structural panel that has just spalled or delaminated is a result of the loss of bond between the concrete and the rebar, and not actually a loss of strength in the steel rebar itself. With post tensioned or pretensioned reinforcement strands this loss of bond and point corrosion are even more critical to the structural integrity of the member. Concrete repair to damaged areas may also increase the corrosion rates directly adjacent to the repair in much the same way as the original damage occurs. Therefore, patching concrete that has suffered distress from chloride induced corrosion without additional mitigating measures further accelerates the corrosion process in the nearby sound concrete. The Federal Highway Administration (FHWA) suggests chloride concentration in concrete less than .15% by weight of cement pose little danger of corrosion and the concrete can be left intact. When the chloride concentration exceeds .3% the concrete should be removed to a level below the rebar or cathodic protection should be applied. In addition, the American Concrete Institute (ACI) places limits on new construction of .15% for standard formed reinforcing bar and .06% for prestressed reinforcing structures. Although the actual corrosion occurring is more clearly defined by a combination of this chloride content and the electrical potential, these chloride levels alone act as a guide to corrosion possibility.

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Since corrosion is an electrochemical process, the probability of corrosion activity is generally indicated by the electric potential of the rebar in reference to a standard electrode contacting the concrete electrolyte (Figure 13).

Figure 13

The probability of corrosion activity is frequently defined in reference to saturated copper-copper sulfate half cell potentials alone using the following criteria: 1. Potentials more negative than -350 millivolts (mv) - high probability of active corrosion. Potentials between -350 mv and -200 mv - uncertain as to corrosion activity. Potentials less negative than -200 mv - high probability of no corrosion activity.

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CORROSION CONTROL Corrosion can be mitigated by any one or a combination of the following methods: 1. Selecting corrosion resistant materials (stainless alloys, PVC, fiberglass, etc.).

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Altering the environment (select backfill around buried tanks and piping). Utilizing coatings and linings that electrically insulate the structure from the electrolyte (paints, plastic films, etc.). Implementing cathodic protection.

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Material Selection Implementation of Method 1 requires a complete new installation. Selection of nonmetal materials certainly solves many corrosion problems but costs are generally higher, special construction considerations must be followed and future construction activity may cause a higher frequency of mechanical failures to occur. Fiberglass resins must also be selected which do not react with active hydrocarbon constituents. Environmental Method 2 is a practical technique for corrosion control when an altered environment can be economically implemented. That technique is recommended for tank burial and piping installations when the native backfill is found to be corrosive. Select backfill is used to provide both a more passive environment and to protect coatings from damage by very active environments. Granular backfill materials provide a homogeneous and high resistivity environment when placed but local chemistry is leached into the excavation by ground water and the select backfill chemistry slowly changes to resemble the native environment. Granular fill placed above grade for AST installations provides good corrosion protection when chloride free highly resistant materials are used and moisture levels are maintained at low levels. Coatings Method 3 is normally not recommended alone since coatings are not perfect and corrosion can simply be concentrated at imperfections. However, coatings are quite effective for atmospheric corrosion control and must simply be maintained for good service. On buried structures, coatings are effectively used with cathodic protection because coatings and cathodic protection act in synergism to prevent corrosion. The cathodic protection system extends the coating life expectancy while the coating reduces the protective current requirement of cathodic protection. Cathodic Protection Cathodic protection (Method 4) prevents corrosion by utilizing an external source of electrical current which forces the entire structure to become a cathode. A corrosion cell operates by discharging current at the anode where metal is damaged and collecting current at the cathode where metal is protected. Cathodic protection provides current from an outside source which is collected on all surfaces of the buried or submerged structure. When sufficient external current flows to the structure, it exceeds any currents which may naturally leave at the

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anodes. The result is a net current flow onto all parts of the structure, which by definition is cathodic protection (Figure 14).

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CATHODIC PROTECTION

Figure 14

The external power source for cathodic protection may include either the natural galvanic metallic couple with a sacrificial metal or the operation of an impressed current system using a rectifier and anodes. Sacrificial (Galvanic) Sacrificial cathodic protection systems typically use aluminum, zinc or magnesium alloys as the anode. Due to their positions on the galvanic series with respect to mild steel, these materials naturally corrode when connected to steel and provide the required electric current for cathodic protection. Sacrificial anode current is limited by the alloy selected, geometry of the anode, the resistivity of the environment and the potential of the buried or submerged structure. The life expectancy of the anode depends on the alloy selected, geometry of the anode and the amount of current discharged. Sacrificial systems are normally limited to well coated and small structures located in an environment with low soil resistivity or marine structures. Impressed Current Impressed current anode properties are essentially the reverse of galvanic anodes. These anodes are relatively non-consumable and are used as current emitting surfaces only when powered by an outside source. Common impressed current anodes in use today include graphite, 13

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high silicon cast iron, lead silver, platinized titanium or niobium and mixed metal oxide. Impressed current systems are free of the limited "driving voltage" associated with sacrificial anodes as they derive their power from a rectifier connected to an external AC source (Figure 15).

Figure 15

A rectifier converts available AC power to low voltage DC power. Most cathodic protection rectifiers are provided with a means to vary the DC output voltage in small increments, or in some cases offer complete control from zero to 100% of rated DC output. Impressed current systems therefore have fewer restrictions in their employment and are used where sacrificial systems are not economically or physically applicable.

Cathodic Protection Design It is the responsibility of the corrosion engineer or technician to adequately define the system he or she is charged to protect. Typically, the designer shall provide a system that is both technically and economically justifiable to the client's needs. The client should be provided with a complete technical description and maintenance and/or monitoring information to ensure proper functioning of a cathodic protection system. Typically, the designer will be addressing the following questions. What is required to be protected? Is the system isolated from other structures in the ground or is it insulated?

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Is the system bare or coated? What type of cathodic protection system is required? What is the protective current requirement? If an impressed current system is required, is appropriate AC power available? How will a working cathodic protection system affect other adjacent buried structures? What type of monitoring and/or testing procedures will this system require? What are the client's requirements concerning design life? What cathodic protection criteria shall be employed for this system? What are the installation requirements for this project? Will this installation interfere with the client's normal operations? Are there adequate drawings concerning the system and other buried facilities at this location? Cathodic Protection Criteria When a structure is under the influence of cathodic protection, chemical reactions are forced to take place on the metal surface. These chemical reactions essentially act as a coating barrier between the structure and its electrolyte. This chemical barrier buildup is commonly called "cathodic polarization". In effect, cathodic protection acts to protect a structure in the same way an applied coating does, except cathodic protection provides a coating that can be continually replenished. This "cathodic polarization" is a physical phenomenon that can be measured. A reference electrode in conjunction with a high internal resistance voltmeter is required to measure the potential of a buried or submerged structure. The most common portable reference electrode in use is a copper-copper sulfate half cell. This is simply a pure copper rod immersed in a saturated solution of its own ions. The copper rod and ionic solution are equipped with a porous plug that becomes solution saturated and allows contact with the earth or seawater. When a voltmeter is connected between the half cell and structure, a potential is measured. This potential is actually a combination of two half cell potentials; that of the reversible copper to copper sulfate potential and the metal structure to earth or water potential. Each of these potentials represents a portion of the total cell potential between the structure, through the electrolyte, to the copper rod.

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A buried or submerged metal structure will always exhibit a potential to earth which is essentially a measurement of the voltage drop across the natural resistance between structure and earth. This potential is the "native" or "static" potential of a structure. The "polarized" potential change of a structure to earth results when a structure is under the influence of cathodic protection. This increase in potential, due to the application of cathodic protection current, is therefore caused by the cathodic chemical reactions (added resistance) taking place on the metal surface. Ideally the reference electrode should be placed immediately adjacent to the structure/electrolyte interface when a potential is measured. Since corrosion testing often involves potential measurements on buried structures, the placement of the half cell at the metal/electrolyte interface is not normally practical. A portable half cell, in most cases, is placed on the surface of the ground as close to the structure as possible. In some instances, permanent test station locations can be installed so that a portable cell can be lowered close to the structure surface or "permanent" reference electrodes can be placed adjacent to a buried structure during the installation phase (Figure 16).

Figure 16

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Cathodic Protection Installation Cathodic protection, when properly installed and maintained, will completely eliminate external corrosion damage to a buried or submerged metal structure. It can extend the life of a steel structure indefinitely, regardless of whether it is coated or not. The installation of a new structure is usually more economical when combining the use of coatings and cathodic protection. However, on an existing structure, a larger cathodic protection system can be designed to protect the structure regardless of the coating condition. For many years cathodic protection has been used to mitigate corrosion damage to gas and petroleum product transmission pipelines. In fact, the U.S. Department of Transportation (DOT) regulations require cathodic protection of these pipelines and contain performance and maintenance standards for such systems. Recent Environmental Protection Agency (EPA) uniform codes and standards mandate the design of corrosion protection for buried steel storage tanks. Complete cathodic protection (and the resultant benefits) is achieved when the protected potential criteria are met at the electrolyte/structure interface over the entire surface of the intended structure. The installation of a few galvanic anodes or the operation of an impressed current rectifier without specific control over the amount of current and the location of current collection will not produce the desired protected effect. A review of common practice for cathodic protection of underground storage tanks (USTs) is helpful. The techniques for the effective protection of USTs are different than conventional pipeline cathodic protection techniques because of the difficulty in current distribution and electrical continuity. Providing uniform and adequate current to all surfaces of the USTs is particularly difficult because they normally are closely spaced and near a large number of foreign structures. Product, vent, water and air lines are frequently in close proximity to the tanks and are either subject to possible interference problems (if isolated) or consume protective current intended for the storage tanks. The bonding of all appurtenant structures or the isolation and control of interference currents for them are usually the most time consuming and difficult part of a UST cathodic protection installation. During the early years of UST cathodic protection, conventional pipeline groundbed techniques were utilized. A remote anode bed was usually installed near the edge of the property, which was then connected, to a rectifier with the negative terminal grounded to the vent piping or electrical conduit, which was to be made electrically continuous to the tanks. This particular technique was employed because it was obviously the least expensive. However, in most cases the complete protection of the tanks could not be achieved in the shielded areas between the tanks. Often ground conditions and the physical limits of the property size did not allow room for a conventional groundbed of low enough resistance to assure reasonable rectifier output voltage. This led to increased interference problems, both on the property and to nearby structures. These problems led to the use of "close", conventional vertically or horizontally installed systems. In these systems anodes were distributed around the tank field to eliminate shielded areas and concentrate the current sources near the intended structures.

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There are a large number of variables to be considered during design of cathodic protection for any structure. If considering only USTs, there is a wide range of current requirements. The current required for complete protection for a buried 10,000 gallon tank can vary from about 2 amperes (for a poorly coated tank) to less than 50 ma for a very well coated tank. It is very difficult to provide long term isolation for tanks in a congested area. For this reason, and because of interference considerations, structures are frequently electrically bonded and protected as one electrically continuous structure. Common practice for cathodic protection of loading docks is quite different from UST installations. The most obvious difference includes dramatically larger current requirements. Docks require from 100 to 3,000 amps of protective current for complete protection depending upon size, geometry, water characteristics and coatings. The anodes are either placed into the water as sleds, pile mounted or drilled deep into the soil near the dock. The rectifiers are likewise considerably larger, often oil cooled and utilizing explosion proof hardware. When galvanic anodes are utilized for protection of marina facilities, they are usually quite bulky ranging up to 1,000 pounds and are either placed on sleds or welded directly to the piles. Hybrid cathodic protection systems utilizing both impressed current and galvanic designs simultaneously on a common structure can often be effectively operated for optimum corrosion control performance.

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