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Cathodic Protection

Overview Cathodic Protection is a corrosion mitigation technique first introduced in the British navy in the 1820s to protect ships in seawater. This corrosion mitigation technique supplies electrons to the corroding metal to suppress metal corrosion and dissolution. Current is supplied by applying a potential usually relative to a reference electrode to the structure that is more negative than the corrosion potential. One of two methods is used to supply the current (control the potential). The first is to use an external power supply. The second is to galvanically couple the structure to an alloy that is more active electrochemically than the alloy of the structure. Cathodic protection has been used to protect steel in concrete, structures such as tankage and piping that are below ground, and ship hulls and other structures in seawater. Two references which provide introductory information and examples are "Corrosion Engineering", M. G. Fontana, Mc-Graw Hill Book Company, New York, 1986 and "Cathodic Protection", R. Heidersbach, Volume 13A, Metals Handbook, ASM International, 2003. The latter reference provides information on pertinent design calculations. Also, numerous web sites exist with company specific information. Theory When a metal corrodes freely as, for example, a piece of steel in the presence of water, the metal undergoes several electrochemical processes. The metal is oxidized to metal ion, solid metal oxide, or metal hydroxide, i.e. the anodic reaction. Balancing that electrochemical reaction is the simultaneous reduction of some species on the metal surface, for example oxygen reduced to water or hydrogen ion reduced to hydrogen gas, i.e. the cathodic reaction. Multiple anodic and cathodic reactions can proceed simultaneously. These reactions proceed to produce the normally measured corrosion rate when the system is allowed to corrode freely, i.e. without external artificial influences. The potential at which these reactions proceed in this manner is the corrosion potential. When a potential is applied cathodic or active with respect to the corrosion potential, the anodic or oxidation reactions are depressed and the cathodic or reduction reactions are accelerated. The applied current required to cause this effect is the basis for the cathodic protection current. This relationship is illustrated in the following idealized partial polarization curve which shows the overall anodic and cathodic reactions. Note that only the solid portion is observed when a polarization curve is measured. Further information on generating polarization scans can be found in http://www.argentumsolutions.com/tutorials/polexpert_tutorialpg3.html

As shown in the above figure, at the corrosion potential the oxidation and reduction reactions proceed at the same rate. When the potential is artificially changed to the point labeled as the Control potential the reduction reaction rate (current) is much greater than the oxidation reaction rate (current). In order to maintain the potential at that point, the current difference between the two reactions is supplied artificially. This cathodic current is the theoretical cathodic protection current at that controlled potential. Note that the anodic or oxidation reaction still proceeds albeit at a much lower rate than under conditions in which there is no applied potential. Practice The cathodic protection current can be generated in two ways, using an external power source supplying current (impressed current) or coupling the structure to a more active alloy whose corrosion supplies the current (galvanic current). Impressed Current Cathodic protection systems that use impressed current might be depicted as in this figure:

The negative terminal of the power supply is connected to the structure to be protected. The positive terminal is connected to the anode which is often made from an inert material e.g. graphite. The power supply provides the current. The circuit is completed through the medium such as soil or water which surrounds the structure and anode. In applications such as protection in soils or seawater the structure is often polarized to a potential relative to a reference electrode. The potential chosen is known to induce protection for that alloy and structure. One of the most common reference electrodes used for this purpose is the copper/copper sulfate reference electrode (http://www.argentumsolutions.com/tutorials/refelectrode_tutorialpg10.html). As an example, a voltage sometimes reported in the literature for protecting steel is approximately -0.85V relative to the copper sulfate reference electrode. Galvanic Current Cathodic protection systems that use galvanic coupling to a more active material might be depicted as in this figure:

The structure is directly connected to an anode such as magnesium, both of which are in the same medium. Corrosion of the anode provides the current to protect the structure. The name sacrificial anode is often applied to this type of anode. The circuit is completed through the medium such as soil or water that surrounds the structure and anode. Sometimes measurement of the potential relative to a reference electrode such as the copper/copper sulfate reference electrode (http://www.argentumsolutions.com/tutorials/refelectrode_tutorialpg10.html) is used to guide the number and size of the sacrificial anodes. Additional Considerations

Stray current is current in the earth generated by a source other than the cathodic protection system that affects the structure being protected. For example, in areas where many buried pipelines might exist, the current protecting one pipeline may adversely affect another underground structure nearby. The operating conditions are, for the most part, determined by testing. Appropriate voltages and currents can usually not be determined a priori.

The -0.85V vs copper/copper sulfate voltage mentioned to protect steel structures does not compensate for the voltage drop between the measuring point of the reference electrode and the structure. This voltage drop can be large in environments with large electrical resistivity.

Reference electrode contamination can become an issue in some environments. A different reference electrode such as a silver/silver chloride reference electrode (http://test.argentumsolutions.com/tutorials/refelectrode_tutorialpg5.html) can sometimes be used as an alternative. Some examples of sacrificial anode materials are magnesium, zinc, aluminum, and aluminum-zinc-tin alloy. Some examples of inert anode materials are silicon-cast iron, graphite, lead, and mixed metal oxides

Anodic Protection Overview Anodic Protection is a corrosion mitigation technique first introduced in the 1960's in which the potential of an alloy is controlled relative to a stable reference potential in a range of values more positive or oxidizing than the corrosion potential that causes the corrosion rate to be depressed relative to that which would occur without the application of the potential. One of the major applications of this technique is the protection of carbon steel or 304 or 316 stainless steel in concentrated (greater than 93 wt%) sulfuric acid. Other applications have been reported in the literature. One excellent though dated reference that provides background on theory and practice is "Anodic Protection", O. L. Riggs and C. E. Locke, Plenum Press, New York, 1981. Further information can be found in "Corrosion Engineering", M. G. Fontana, Mc-Graw Hill Book Company, New York, 1986. Theory Certain alloys in certain conductive environments exhibit a characteristic in which as the potential is increased (relative to a reference electrode) in the anodic or oxidizing direction, the current increases until a potential is reached in which the current exhibits a rather abrupt decrease. Further increases in potential do not result in much increase in current until a much higher potential is reached. This characteristic is shown in this idealized potentiodynamic polarization scan:

As shown in this figure, the potential at which the current shows an abrupt decrease is known as the primary passivation potential. Chemically what is often occurring as that the oxidation reaction is changing, for example instead of iron metal reacting with the environment to form iron in a +2 valence state, iron reacts with the environment to form iron in a +3 state. The resulting oxidation product on the surface is more corrosion resistant. Controlling the potential above or anodic to this point tends to maintain the current at this low value. This current is the new rate of corrosion. Since the abscissa of the plot is the logarithm of current, the decrease in corrosion can be several orders of magnitude. Anodic protection is the technique in which the potential is controlled in this low corrosion regime. Information on how to generate these polarization scans can be found at (http://www.argentumsolutions.com/tutorials/polexpert_tutorialpg3.html). An estimate of the steady state current in this more passive regime is sometimes obtained by performing controlled potential tests lasting several days to several weeks. Practice Conceptually, the equipment used for anodic protection is straightforward. The following figure shows a simple arrangement of the equipment that might be used for a vessel:

The "Power Supply & Voltmeter" acts somewhat like a potentiostat in that it provides the current to the cathode so that the sensing point of the reference electrode is at the desired control potential. This potential is chosen so that the potential of the vessel surface is in the "passive" region for the alloy being protected. The current flows between the cathode(s) and the vessel. The number of cathodes and their position often depends on the geometry of the installation. The goal is to try to maintain all interior areas of equipment exposed to the liquid environment within this passive region. Though the current requirements to maintain anodic protection tend to be low, the amount of current needed to get the alloy to the state of protection can be large. The above figure in the first section shows the reason. The potential of the alloy when it initially contacts the environment is at the corrosion potential. As the potential is increased, the current follows the curve in the above figure. The required maximum current applied to force the alloy above the primary passivation potential (the current at the primary passivation potential) can be several orders of magnitude above the current required for control. This need has implications in the design (size) of the power supply needed for anodic protection. Anodic protection has been proposed to protect iron and stainless steels in a number of environments some of which are shown below.

Stainless steel heat exchangers used for handling concentrated sulfuric acid Cast iron in boiling sulfuric acid Certain stainless steels in acetic acid Mild steel in certain types of phosphate containing fertilizers

Certain steels and stainless steels in phosphoric acid in plants and tankers

One characteristic of these environments is that they usually do not induce pitting or other types of localized corrosion. Control of potential above the corrosion potential may induce localized corrosion if the environment contains agents (e.g. chloride) that are known to initiate localized corrosion of the alloy being protected. Further information can be found in the references in the Overview section above.

Inhibition

1 Overview 2 Types of Corrosion Inhibitors 2.1 Film Alteration Formers or Environment

2.2 Anodic, Cathodic, or Mixed Inhibitors 2.3 Organic or Inorganic Overview Corrosion inhibition involves the addition of a chemical to the environment to make the environment less aggressive or to protect the metal. Since the chemicals are added to the environment, this approach is often used for closed systems which are not open to the atmosphere. Examples are recirculated cooling water systems or acid pickling baths. Corrosion inhibitors are also added into organic coatings, and can be released to alter the local environment for a coating exposed under atmospheric conditions. One reference with many examples of corrosion inhibitors, the metals they are used for, and the mechanisms by which they act is "Organic Corrosion Inhibitors" by Y. I. Kuznetsov, Plenum Press, New York, 1996". Types of Corrosion Inhibitors Corrosion inhibitors can be categorized in different ways: Film Formers or Environment Alteration

Film forming inhibitors that act by forming a protective film on the surface by adsorbing on the surface and thereby block the environment.

An example is the inhibition of copper corrosion by benzotriazole or tolyltriazole in which these molecules adsorb on the copper surface to protect the copper metal below the film.

Film forming inhibitors that act by reacting with the metal surface to create a passive layer between the metal and the environment.

An example is the inhibition of carbon steel in water by phosphonate type compounds in which the phosphonate acts by reaction with the metal and components in the water (such as calcium) to create a more impervious passive layer on the steel surface. Molecules that act by removing aggressive species from the environment by reacting with them. such as oxygen getters that remove dissolved oxygen

Inhibitors that alter the environment

Oxygen which can be an aggressive corrosion agent has been removed by this procedure. Examples of molecules that can react with oxygen are sodium sulfite and hydrazine. These agents are sometimes called oxygen getters. Borate is an example of a common buffer This approach can be dangerous and should be used with caution. For example, too much oxidizing power could result in the corrosion potential of the metal being pushed into a region in which pitting or stress corrosion cracking could be more prone to initiate.

Buffer the environment to prevent changes in acidity (pH shifts)

Provide oxidizing power to the environment to passivate the metal.

Anodic, Cathodic, or Mixed Inhibitors These types of inhibitors act by interfering with parts of the corrosion reaction. They are classified in the following way:

Anodic inhibitors primarily slows the reaction kinetics of the anodic reaction. The corrosion potential is usually shifted in the positive direction. Cathodic inhibitors primarily slows the reaction kinetics of the cathodic reaction. The corrosion potential is usually shifted in the negative direction. Mixed inhibitors tend to slow the reaction kinetics of both the anodic and cathodic reactions about equally. The corrosion potential may or may not shift.

Organic or Inorganic

Organic inhibitors are commonly used in acid solutions and they usually act by inhibiting the cathodic reaction. A common application is acid pickling which is used to remove oxide scale from steel ingots. Acids chemically dissolve the oxide scales, and

inhibitors are needed to inhibit the electrochemical dissolution of the metal after the scale is removed.

Inorganic inhibitors are commonly used in neutral to alkaline environments and they usually act by forming a film and inhibiting the anodic reaction.

chromate is a common inorganic inhibitor that is a film former (but it also inhibits the cathodic reaction)