Galvanic

Harvey P. H a c k ~

BASIC PRINCIPLES
Electrochemical Reactions
IN ORDER TO BE able to properly design and interpret the results from galvanic corrosion tests, it is necessary to have some appreciation of the electrochemical theory behind galvanic corrosion. Metal corrosion consists of at least two reactions. The first is the metal going into solution in the electrolyte M ---~M n+ + n e For iron in steel corroding in water at room temperature, this reaction would be Fe ~ Fe 2+ + 2eSince the metal is transformed from an atom with no net charge to an ion in solution with a net positive charge, this type of reaction is called an oxidation reaction, and generates electrons. Oxygen need not be involved in an oxidation reaction, only a net increase in charge of the metal. The oxidation reaction involved in the corrosion process is also called the anodic reaction. Since electrons are generated by the oxidation reaction, and since there can be no net accumulation of charge in these reactions, there must be another reaction occurring that uses up these electrons. This is the cathodic or reduction reaction, and it will always result in some species reducing its charge as it gains electrons. The three c o m m o n reduction reactions in water are hydrogen reduction, occurring primarily in acids 2H + + 2e- --+ H2(gas ) oxygen reduction occurring primarily in acids 02 + 4H + 4e- ~ 2H20 and oxygen reduction occurring primarily in bases or neutral water
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oxygen molecules that are dissolved in the water. Other reduction reactions not illustrated include metal ion reduction and plating. M1 of these reactions generate or use up electrons and, therefore, involve the flow of a current. For this reason, they are called electrochemical reactions, and their rates are influenced by externally applied currents and potentials. For example, if electrons are forcibly removed from the anodic corrosion reaction, the reaction will occur more rapidly. Removing electrons also causes the potential of the corroding metal, as measured relative to a device with a very stable potential called a reference electrode, to become more positive. This is plotted in Fig. 1. The relationship is illustrated as a straight line where potential is plotted against the log of the reaction rate. This straight-line relationship was first noted by Tafel [1], and the slope of the line honors him by being called the Tafel slope. Anodic reactions usually have a positive Tafel slope. Ideal reactions frequently yield these straight lines, but in practice it is c o m m o n to see curved lines. The process of changing potential by applying a current is called polarization. The cathodic reactions can also be plotted on the same type of graph. Adding electrons to the hydrogen reduction reaction (or to any cathodic reaction) will speed up that reaction and shift the potential more negative. This is shown in Fig. 1 as another straight line with a negative Tafel slope. Electrochemical reactions generate or use up electrons, and therefore, the rate of a reaction is equivalent to the electron current generated or used up by that reaction.

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The first of these cathodic reactions generates hydrogen gas and is readily observed when zinc or iron are placed in certain strong acids. The last two cathodic reactions use
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FIG. 1--Evans diagram for iron in an acid.

234

C O R R O S I O N T E S T S AND S T A N D A R D S M A N U A L
ACTIVE ENO (-)

Galvanic Series Since no charge can accumulate on any metal surface, the electrons generated by the anodic reaction must all be used up by the cathodic reaction. This can only occur in Fig. 1 where the anodic and cathodic reaction lines cross. At this point, the rate of the anodic reaction, the corrosion rate, equals the rate of the cathodic r e a c t i o n - - i n this case, hydrogen generation. This rate is called the open-circuit corrosion rate, abbreviated ico~:. The potential at which the lines cross is called the open-circuit corrosion potential, abbreviated E~or~. This type of plot is called an Evans Diagram, after U. R. Evans, a pioneer in corrosion electrochemistry. Any corroding metal should, u n d e r open-circuit conditions, exist at E~orr corroding at a rate io~r, which can be predicted from the Evans Diagram. The value of E~or~will depend on the position of the curves. The anodic curve is a function of the type of metal and the charge it receives when it goes into solution. The cathodic curve is a function of the type of cathodic reaction, the type of surface on which that reaction takes place, the concentration of reacting species, and other factors, most of which are dependent on the environment in which the metal sits.
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Each metal/environment combination, therefore, exists at a unique potential. For a given environment, the potentials of various materials can be listed in a form called a galvanic series. Galvanic series can be expressed either as a graph giving the numerical values of the potentials of the materials in the given environment, as in Fig. 2, or as a list in order of increasing or decreasing potential without the specific values, as in Fig. 3. The galvanic series is important because it helps to predict what happens when two metals are placed in electrical contact in that environment. The metal that is more negative in the galvanic series will have

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CHAPTER 20--GALVANIC
a driving force to lose electrons to a metal in electrical contact that is more positive in the series. This will cause the corrosion rate of the more negative metal to increase when the electrical connection is made. It is this increase in corrosion of the more negative metal u p o n contact with a more positive metal that is called galvanic corrosion. The galvanic series allows prediction of which of the metals in contact, the galvanic couple, will suffer increased corrosion.

235

those reactions. The zinc corrosion rate has increased from Icorr,Zn to Icoupled, Zn" This increase is the galvanic corrosion rate. The iron corrosion rate has decreased from Ico~,Fe to Icoup]ed,Fe-This decrease is called cathodic protection.

Effects of Anode/Cathode Area Ratio

There was a shift in axis labeling between Figs. 4 and 1. Figure 1 expressed reaction rate as lower case i, the reaction current per unit area, which is appropriate for considering single metals. Figure 4 was forced to switch to total reaction current I, because it is the total current from each metal that must be considered in the summation. The effect of changing the relative areas of the anode and cathode is illustrated in Fig. 5. If the cathode is small, the original Evans diagram for the cathodic material must have the current densities multiplied by a small area to obtain total currents. This makes the lines appear far to the left in Fig. 5, and results in only a small increase in anodic corrosion rate, Icoupled,anod .... all cathode, over /co. . . . . de" If the cathode is large, the original Evans diagram for the cathodic material must have the current densities multiplied by a large area to obtain total currents. This makes the lines appear far to the right in Fig. 5, and results in a large increase in anodic corrosion rate, /coupled,anode,large cathode, o v e r /corr,anode" This illustrates the area ratio effect in galvanic corrosion. A small anode and large cathode result in a large anodic corrosion rate, whereas a large anode and small cathode are far more desirable.

Mixed Potential Theory

It is tempting to say that the farther apart two metals are in the galvanic series, the more corrosion will occur on the more negative material, or anode. Unfortunately, this is not the case. In order to predict the rate of galvanic corrosion, an Evans Diagram of both metals involved must be considered. This approach is called Mixed Potential Theory. In Fig. 4, Evans Diagrams are shown for two materials of equal surface area that have different potentials on the galvanic series in an acid: iron and zinc. The anodic material, zinc with the more negative E .... z,, corrodes uncoupled at a rate of Icorr.Z~" The cathodic material, iron with the more positive Ecorr,Fe, corrodes uncoupled at a rate of /corr,Fe. When these metals are electrically connected, electrons can flow between them, upsetting their individual balances. Since there are four reactions to consider, and since electrons can now flow freely between all four reactions, the charge balance must be handled differently than for the individual metals. All of the electrons generated by the anodic reactions must still be consumed by the cathodic reactions. Therefore, the sum of the anodic reactions is plotted as a dashed line with a positive Tafel slope, and the sum of the cathodic reactions is plotted as a dashed line with a negative Tafel slope. The intersection of these two sum lines is where all charges balance, and the potential so defined is called the mixed potential of the galvanic couple, or coupled potential, Ecouple. The mixed potential of the couple is shown as a dotted line in Fig. 4. The points where the individual reaction lines cross the mixed potential define the rates of

Flow Rate
Changing the electrolyte flow rate can have significant effects on the curves in the Evans diagram, and therefore, can dramatically influence galvanic corrosion rate. The direction of the effect can only be predicted using Evans diagrams, however. If the cathodic reaction is oxygen reduction rather than hydrogen reduction, oxygen must be supplied to the metal surface by diffusion in order to react. Diffusion can be a slow process relative to the electron exchange, and this can make the cathodic line in the Evans diagram deviate from
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236

C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

the current will then rise sharply. This is shown in Fig. 7. Some of the most protective passivating corrosion products are on stainless steels. These films form m o r e readily in the presence of oxygen, and so are enhanced by flow. This leads to the situation shown in Fig. 8 where increasing flow increases oxygen delivery, which increases the a m o u n t of protective corrosion products, lowering the anodic currents. This can cause corrosion rates in a galvanic couple to decrease with increasing flow, opposite to the oxygen effect on the cathodic reaction discussed above.

a straight line. Oxygen diffusion occurs through a relatively stationary b o u n d a r y layer, which becomes thinner as flow increases. Diffusion rate therefore increases with flow, and the m a x i m u m rate of the oxygen reduction reaction, i L, increases with flow. This is shown in Fig. 6. When the diffusion-limited cathodic curve is present in a galvanic couple, the total cathodic current will increase with increasing flow, causing corrosion rate of the anode to increase with increasing flow. Flow can also have an effect on the anodic reaction. Many materials exhibit passivity, which causes the anodic reaction to deviate dramatically from a straight line. This is caused by the corrosion products formed during the anodic reaction becoming firmly attached to the metal surface, blocking the reaction from proceeding further. The anodic line in the Evans diagram will be straight until the corrosion product forms, after which the current will rapidly drop even though potential is still increasing. The low current will persist until the potential becomes sufficiently positive to break down the corrosion product or to produce oxygen directly from water by electrolysis. In either event,

Measured Currents
Much of the current that flows between reactions in a galvanic couple will flow between the anodic and cathodic metals, but some also flows within these metals. Internal current is not directly measurable, although it can be inferred from other test methods that use external current that can be measured. Measurable external currents can be predicted from the Evans diagrams as follows. When a metal is corroding by itself, as in Fig. 9, the corrosion current is i . . . . which flows entirely between anodic and cathodic sites in the metal and cannot be measured. All

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Log Current Density FIG. 8--Effect of flow on passivity.

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Log Current FIG. 9--Creating polarization curves from Evans diagrams.

CHAPTER 20---GALVANIC

237

electrons produced by the anodic reaction are consumed by the cathodic reaction. If an external source, such as a power supply or another metal electrically connected to the first, removes electrons, the anodic reaction will increase to supply more electrons and the cathodic reaction will decrease to use up less electrons. The externally applied anodic current will be the difference between the anodic and cathodic reaction currents. At very positive potentials, the cathodic current will be negligible, and the applied current will roughly equal the anodic corrosion rate. At very negative potentials, the anodic current will be negligible, and the applied current will roughly equal the cathodic current. At Ecorr the external current will be zero. The externally applied current will follow a shape called a polarization curve, shown in Fig. 9. Galvanic corrosion rate can be roughly predicted by superimposing the polarization curves of the anodic and cathodic materials. This is shown in Fig. 10. W h e n the open-circuit potentials of the anode and cathode are relatively far apart, more than roughly 120 mV depending on the slopes of the curves, this prediction is fairly accurate. The polarization curves for the anodic and cathodic materials are multiplied by their respective wetted surface areas and placed on the diagram. The intersection of the anodic curve for the anodic material with the cathodic curve for the cathodic material provides an indication of the galvanic corrosion rate,/galvanic, and the exact coupled potential, Ecouple.

law of I1R 1. Current 12 must travel farther, through an increased resistance R 2, and will therefore be smaller than I]. The voltage drop here is I2R 2. The largest distance is traversed by current 14, through the largest resistance R4, and will therefore be the smallest current and undergo a vokage drop of I4R4. The falloff of current (and corrosion rate) as distance from the second metal increases is a comm o n method for recognizing galvanic corrosion. Although current decreases with distance, the product of current times resistance will increase with distance. The largest vokage drop in this example would be 14R 4 and the smallest would be I1R 1. The voltage drops are shown in Fig. 11. The presence of an IR drop not only decreases the current on the anodic and cathodic materials, but also allows the anode to be at a different potential than the cathode. The potent/Ms will be closest to Eco,ple where the anode and cathode are closest, and will shift towards Eoo~Tfor each material as separation distance increases. This creates a potential distribution over the structure that can he measured.

Factors C o n t r o l l i n g Galvanic C o r r o s i o n
Any factor that controls corrosion of a single metal m a y control galvanic corrosion by its effect on one or more of the reaction lines on the Evans diagram. Besides flow and pH, these factors include temperature, electrolyte composition, surface condition of the metals, thermomechanical and potential history of the surfaces, and m a n y more too numerous to mention. Factors unique to galvanic corrosion include anode/cathode area ratio, electrolyte resistivity, and geometry. Sometimes it is important to know which reactions control or limit galvanic corrosion rates. The polarization curves in Fig. 12a illustrate how a diffusion-limited cathodic reaction will control the rate of galvanic corrosion. Changing the shape of the anodic polarization curve, for example, by the use of an anodic inhibitor, has no effect on galvanic corrosion rate determined by the curve intersection, whereas changes in the cathodic diffusion-limited current result in equivalent changes in galvanic corrosion rate. Similarly, galvanic corrosion of passive materials, as

Current a n d P o t e n t i a l D i s t r i b u t i o n s
For galvanic corrosion to occur, there must exist at least two metals with different corrosion potentials, a metal path for electrons to flow between them, and an ionic path through the electrolyte to complete the electronic circuit. The latter is sometimes not considered, but contributes to nonuniformity of galvanic current and potential on large structures. Figure 11 shows two metals electrically connected in an electrolyte that has a significant resistivity, such as tap water. Current 11 must travel through some small electrolyte resistance R 1 to go the short distance from the anode to the cathode, and undergoes a voltage drop according to Ohm's

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238

C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

b) Anodlc Control C) Mixed Control

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FIG. 12--Type of control of galvanic corrosion reactions: (a) cathodic control; (b) anodic control; (c) mixed control, shown in Fig. 12b, is frequently under anodic control, with the shape of the cathodic polarization curve making little difference. Mixed control as in Fig. 12c is also possible.

TESTING TECHNIQUES Exposure of Galvanic Couples

The most obvious method of testing for galvanic corrosion is to construct a couple between the materials of interest and place it in the environment of interest. Material condition, environment, and geometry should simulate the application as closely as possible. Care should be taken during assembly to ensure adequate electrical connection, and this connection should be checked before, after, and occasionally during the exposure using an appropriate ohmmeter. In some cases, it m a y be possible to electrically isolate the individual metals from each other and connect t h e m through an external wire, which can be used to measure galvanic current during exposure. For small specimens it is permissible to use a 1-f~ resistor in the line to measure voltage drop and calculate current. Where currents are larger or where corrosion potentials are close for the materials involved, use of a zero-resistance a m m e t e r m a y be more appropriate for current measurement. The potential of the couple can also usually be monitored during the exposure using a suitable reference electrode. More detail on galvanic corrosion testing in electrolytes can be found in ASTM G 71, Guide for Conducting and Evaluating Galvanic Corrosion Tests in Electrolytes. I m p o r t a n t material factors to consider when simulating a galvanic corrosion situation include chemical composition, thermal history, and surface condition. Changes in these parameters m a y change the corrosion behavior of a material when it is not in a galvanic couple without affecting its galvanic corrosion behavior, or may affect its galvanic corrosion behavior without a significant effect on its corrosion properties when it is used alone. Any environmental factor that can influence corrosion can also affect galvanic corrosion. Environmental factors to consider when designing a test include major chemical components, dissolved gases, m i n o r constituents, organic materials, biological organisms and activity, temperature, flow, and electrical conductivity. In atmospheric galvanic couples, atmospheric factors such as time-of-wetness, orientation relative to prevailing winds, sunlight exposure, height above ground, and other unique atmospheric conditions should also be considered. Some important atmospheric

factors affecting corrosion are discussed in ASTM G 33, G 50, G 84, and G 92. 2 The relative geometry of the parts of interest in the galvanic couple can also influence corrosion behavior. In low conductivity environments, the distance of separation of the dissimilar metals will affect galvanic corrosion rate. Even in high conductivity environments, it is difficult for galvanic current to travel into long n a r r o w crevices or down the insides of tubes. The relative wetted surface areas of the dissimilar metals will dramatically influence galvanic corrosion rate. In atmospheric exposures, geometry can control water trapping and drainage, and thermal mass, which controls dew retention. Ensuring adequate electrical contact between the dissimilar metals in a galvanic couple can be difficult. Pressure contact, such as between two plates bolted together, is subject to corrosion products forming between the plates and wedging them apart. Attachment of wires by soldering or brazing will work with some materials, but the use of drilled and tapped holes for screw attachment or through holes for bolting m a y be required for others. In some cases, spot welding can be used for electrical attachment. Finally, a wire may be inserted into a drilled hole and the hole peened closed around the wire, although this method is not reliable over long exposure periods. Whatever connection method is used, the connection area and wire are subject to corrosion, which can affect both the electrical contact and the performance of the galvanic couple being tested. For this reason, coatings are frequently used on the connection area. When electrical contact is maintained by physical contact of the dissimilar metals, periodic m e a s u r e m e n t is desirable to ensure that electrical continuity is maintained. If continuity is checked frequently relative to the length of the exposure, it will be possible to adjust the materials to regain this continuity without significantly affecting the results. This should be done without disassembly or gross movement, such as by tightening tensioning bolts. Mounting of galvanic couples for testing should be done carefully using insulator materials to avoid the possibility of establishing electrical continuity with the mounting device or test chamber. Mounting techniques include gasketed seals, rod mounting, epoxy mounting, press-fit, partial immersion, full immersion, and others. The mounting technique chosen is related to the type of corrosion expected, the electrical connection method, the type of exposure desired, presence or absence of water-line effects, and the materials chosen. Duration of exposure is extremely important in galvanic corrosion testing. In m a n y galvanic couples, the a m o u n t of corrosion is highly variable with time. Initial high corrosion rates m a y fall dramatically, initial low rates m a y suddenly increase, and the relationship between anodic and cathodic materials can even reverse with time. For these reasons, the duration of the test exposure should be of sufficient length to ensure that the corrosion processes have reached steady 2ASTM G 33, Practice for Recording Data from Atmospheric Corrosion Tests of Metallic-Coated Steel Specimens; G 50, Practice for Conducting Atmospheric Corrosion Tests on Metals; G 84, Practice for Measurement of Time-of-Wetness on Surfaces Exposed to Wetting Conditions as in Atmospheric Corrosion Testing; G 92, Practice for Characterization of Atmospheric Test Sites.

CHAPTER 2 0 - - G A L V A N I C
state if long-term performance is being evaluated. Test duration should be similar to service duration for shortterm service. In atmospheric testing, the season of the year when exposure is initiated m a y influence the test. Multiple exposures of different time periods may be used to give corrosion rate information as a function of time. Exposures can be conducted on full-scale components or on scaled down or simplified geometries. Full-scale components have a n u m b e r of advantages, including not needing to consider details of geometry and ease of relating the results to service performance. However, full-scale c o m p o n e n t testing may be impractical or too expensive, in which case scale modeled components may have to be used. If scale modeling is used, details of scaling laws must be understood before designing the test. For example, when galvanic corrosion current distribution is important, the conductivity of the electrolyte m a y need to be scaled by the same factor as the physical size. This procedure, called Dimension and Conductivity Scaling (DACS), would involve the use of an electrolyte of one-tenth conductivity for a one-tenth-scale model. DACS scales only p r i m a r y current distribution, which is controlled by IR drop in the electrolyte. Secondary and tertiary current distribution are influenced by polarization behavior of the material involved, and are best approximated by the use of full-conductivity electrolytes. Both types of current distributions cannot be modeled simultaneously, so a decision must be m a d e as to which is most important. Small structures in highly conductive electrolytes should generally be tested in full-conductivity electrolytes, whereas DACS should be used primarily for large structures in low-conductivity electrolytes. To date, DACS has been used primarily for ship cathodic protection system design. More information on scaling can be found in Refs 2 through 5.

239

Electrochemical Tests
Accelerated testing to get a result in a shorter time period than would be possible naturally should be avoided whenever possible, because the mechanism of galvanic corrosion can change if the rate is altered significantly. For this reason, electrochemical tests are frequently chosen to evaluate galvanic corrosion performance. The sensitivity of these tests allows for obtaining results fairly quickly without accelerating the corrosion process. Electrochemical galvanic corrosion tests can be placed into three categories: sensitive galvanic current measurement, galvanic series determination, and polarization curve measurement. Sensitive current m e a s u r e m e n t involves an ordinary galvanic couple exposure, but with current between the dissimilar metals forced to flow through an external wire where it can be measured with a zero-resistance a m m e t e r or by voltage drop across a 1-f~ shunt resistor. This type of testing is described in ASTM G 71. Determination of a galvanic series involves placing the materials of interest from the galvanic couple individually in the environment of interest and monitoring their electrochemical potential over time. The material with the more electronegative potential will become the anode and suffer accelerated corrosion when placed in a galvanic couple. Galvanic series are extremely useful during the materials

selection process to make sure that the anodic areas are large c o m p a r e d to the cathodic areas in complex structures. The galvanic series is influenced by all of the environmental variables described earlier, so the series should only be used if it is developed in the environment in which the galvanic couple will see service. One disadvantage of the galvanic series is that it is frequently misapplied. A series developed in one environment is used to predict performance in another environment. A second disadvantage of the galvanic series is that it does not predict rate. Separation in potential between dissimilar materials does not relate to the rate of corrosion in a couple. More details of the development and use of galvanic series are given in ASTM G 82, Guide for Development and Use of a Galvanic Series for Predicting Galvanic Corrosion Performance. Galvanic corrosion can be predicted by overlaying polarization curves, as described earlier. The determination of polarization curves is, therefore, an important method for galvanic corrosion testing. These curves can be obtained galvanostatically, potentiostatically, or potentiodynamically. Galvanostatic testing is typically used for determining the efficiency of sacrificial anodic materials, such as is done in ASTM G 97, Test Method for Laboratory Evaluation of Magnesium Sacrificial Anode Test Specimens for Underground Applications, or NACE Standard RP0387, Metallurgical and Inspection Requirements for Cast Sacrificial Anodes for Offshore Applications. The most c o m m o n method of obtaining polarization curves is potentiodynamically. Potentiodynamic testing is described in an earlier section of this manual. For galvanic corrosion, the scan rate for these tests should be as slow as possible, since long-term polarization behavior is usually what is sought in predicting long-term galvanic corrosion behavior. Potentiostatic polarization curve generation is advantageous for situations where polarization is time-dependent and prediction of long-term galvanic corrosion performance is desired. This involves exposing a series of individual specimens of each material at a variety of different potentials for a duration sufficient to ensure steady-state behavior. The steady-state current at each potential is obtained, and polarization curves constructed from the potential/current data pairs. Using electrochemical tests to predict galvanic corrosion performance has the same caveats as in any other type of predictive testing. Conditions must be as close as possible to those being modeled. This includes not only solution chemistry and flow, but also the surface condition of the samples. Polished samples can behave quite differently from samples with more representative surface conditions and corrosion products developed by pre-exposure. More detail on using electrochemical tests for galvanic corrosion can be found in Refs 6 and 7.

Computer Modeling
Although not a laboratory testing technique, computer modeling is still an important tool in understanding and predicting galvanic corrosion performance. As mentioned above, exposure of scaled components of a galvanic couple leads to scaling problems in that the p r i m a r y current

240

C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

orientation. Since rainwater and dew are fairly poor electrical conductors, and since they are usually present only as thin layers on the surfaces of materials exposed to the atmosphere, there is a large IR drop between the anode and the cathode in any atmospheric corrosion exposure. This limits the effective distance over which galvanic interactions take place to about 0.5 cm, which in turn means that the effective area ratio of anode to cathode in an atmospheric exposure is almost always about 1:1. The limited electrolyte also makes electrochemical measurements impractical. Atmospheric corrosion typically occurs only during a small percentage of the total exposure time, typically when the surfaces are wet from precipitation, dew, fog, or when hygroscopic compounds on the surface absorb moisture during periods of high humidity. For this reason, atmospheric corrosion occurs slowly, and long exposure durations are usually necessary. Most tests typically involve m i n i m u m durations of 1 to 3 years, with 20 years m a x i m u m exposure not unusual. Tests of shorter duration than one year not only have so little corrosion as to make evaluation of mass loss difficult, but also suffer from the effects of seasonal variation of corrosion rate. Finally, the time that a specimen is wet depends on sunlight heating, prevailing winds, and specimen geometry. S p e c i m e n orientation is, therefore, m u c h m o r e critical in a t m o s p h e r i c galvanic corrosion testing. S t a n d a r d orientations are specified in ASTM G 50 as 30 to the horizontal facing south or the nearest source of c o r r o d e n t (the sea). Three standardized atmospheric galvanic corrosion tests are the plate test, the wire-on-bolt test, and the disk test. The plate test, described in ISO Standard ISO7441, Determination

distribution cannot be scaled at the same time as the secondary and tertiary current distributions. Computer modeling is usually best for making accurate predictions of the distribution of galvanic corrosion over a structure in which both solution IR drop and polarization behavior both control current distribution. Computer models require the geometry of the structure to be input. Additional inputs include the electrolyte conductivity and the polarization behavior of the surfaces of all materials, usually obtained from laboratory testing. Although finite element analysis and finite difference analysis have both been used to predict distribution of galvanic currents on structures, the boundary element technique is becoming the computer tool of choice. This technique requires only that the surfaces of the structure be defined, whereas the other methods require that the volume of the electrolyte be divided into a three-dimensional grid, a time-consuming and difficult process for complex structures. The disadvantage of the b o u n d a r y element method is that at present the commercially available software for performing this analysis is not very user-friendly.

Atmospheric Tests
Unlike galvanic corrosion testing in electrolytes, galvanic corrosion testing in the atmosphere can be standardized because special circumstances exist that limit the n u m b e r of test variables. Three factors that are different in atmospheric testing from most other galvanic corrosion testing are the presence of a limited a m o u n t of electrolyte, the need for a very long duration of exposure, and the importance of specimen
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CHAPTER 20--GALVANIC 241

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of Bimetallic Corrosion in Outdoor Exposure Corrosion Tests, consists of a large plate of the anodic material sandwiched between two small plates of the cathodic material and held together with nonmetallic or insulated bolts. Sometimes the crevice area between the plates is coated with an organic material. The two possible configurations are shown in Fig. 13. Typical exposure durations are 1 to 20 years. At the end of this time, the anodic plate may be evaluated metallographically, visually, by mass loss, or by material property loss (typically using tension testing). The advantages of this test are that materials are usually available in plate form, and a wide range of analyses can be used on the exposed panels. The disadvantages include the need to know which material is the anodic beforehand, the long exposure duration, the difficulty of maintaining electrical continuity between panels, and the possibility of confusing crevice effects with galvanic effects. At one time, ASTM also had a standard for this test method, but dropped this standard due to these disadvantages and lack of use. The wire-on-bolt test, described in ASTM G 116 (Practice for Conducting the Wire-on-Bolt Test for Atmospheric Galvanic Corrosion), has been used with standard materials as an atmospheric corrosivity test under the names of the CLIMAT and ATCORR tests. This test consists of wrapping a 1.0-m length of wire of the anodic material a r o u n d a threaded bolt or rod of the cathodic material. Post-test evaluation is typically done by mass loss only. Since the wire diameter is much smaller than the 0.5-cm galvanic interaction distance in the atmosphere, the effective anodeto-cathode area ratio is well below 1:1, making this a fast test. A typical exposure duration is 90 days. The short duration is
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EVALUATION OF TEST RESULTS

Exposure of Galvanic Couples

If the different materials can be disassembled after testing, mass loss measurements can be performed. In some

FIG. 14--Components for making wire-on-bolt atmospheric exposure assemblies (taken from ASTM G 116).

242

CORROSION TESTS AND STANDARDS MANUAL

cases, loss of strength may also be of interest. If disassembly is not possible, the specimens may still be examined for pitting, cracking, color and extent of corrosion products, and, in some geometries, thickness loss. Mass loss of an assembly m a y still be useful if corrosion of the cathode was minimal. After exposure, destructive techniques such as metallographic examination may also provide information about the extent and morphology of corrosion. Useful standards for cleaning samples after immersion and evaluating mass loss, pitting, and degradation in properties are ASTM G 1, G 46, 3 and G 71. Applying the results of a set of measurements designed to generate a galvanic series is described in ASTM G 82.

profiles deviating in the right places in the right directions. This does not m e a n that the answer is correct, however. Discontinuities in potentials between adjacent areas could be caused by discretization error, resulting from the selection of boundary elements that are too big. The analysis should always be checked to ensure that the total anodic and cathodic currents are equal. Inequality could m e a n a lack of mathematical convergence of the model. The most important check on the results of a computer model occurs before the model is ever run. The input polarization curves must be accurate in order for the model predictions to be meaningful. Model results should be spot-checked against the real structure whenever possible.

Electrochemical Tests
When the potentials of two materials in a galvanic couple are widely separated, Faraday's Law can be used to calculate the galvanic corrosion rate from the galvanic current measured between them. This calculation can be done by the procedures in ASTM G 102. Overlaying of polarization curves of the different materials in a galvanic couple must be done by first converting the current densities into total currents by multiplying the polarization curves by the exposed wetted surface area for each material. The curves then may be overlaid, and if IR drop is not important, the couple current and potential m a y be predicted. If the coupled potential deviates by 50-100 mV from the open-circuit potential of the anode, then the current may be converted by Faraday's Law into a corrosion rate. If the coupled potential deviates by less than 50-100 mV from the open-circuit potential of the anode, then it is conservative to add the open-circuit corrosion rate of the anode to the corrosion rate calculated from Faraday's Law to get the total anodic corrosion rate. Neither of these methods is exactly accurate, but both will give a reasonable approximation to the true corrosion rate of the anode in the couple. If the polarization curve for the anode is known, the coupled potential may be measured to predict corrosion performance. The couple current is the current on the anodic material polarization curve at the measured coupled potential. Corrosion rate may be calculated from the couple current determined in the same way as in the previous paragraph.

Atmospheric Tests
Only mass loss information is obtained from the standard atmospheric galvanic corrosion tests, with the exception of the plate test. The plate test specimens can also be evaluated by metallography, visual examination, probe-type attack depth gages, or mechanical tests such as tensile strength.

STANDARDS
Laboratory testing for galvanic corrosion involves so many variables that it is difficult to write a single standardized test. For this reason, there are no standardized laboratory testing procedures specifically for galvanic corrosion. If another form of corrosion is being studied, then a slight modification to a standardized test for that corrosion form may be used. For example, to study galvanically accelerated stress corrosion testing, ASTM G 30, Practice for Making and Using U-Bend Stress-Corrosion Test Specimens, may be used, adding only a wire between the specimen and a second material to create the galvanic couple. To study the breaking strength of a piece of metal, a standard mechanical pull test such as that found in ASTM E 8, Test Methods for Tension Testing of Metallic Materials, m a y be used. To study the effect of galvanic corrosion on breaking strength, the same test m a y be used on pieces of metal after exposure to the environment of interest, both with and without galvanic coupling to a second material. Subtracting the strength of the metal with galvanic coupling from that without it will give the effect due to galvanic corrosion. There are two guidelines for galvanic corrosion testing published by ASTM: ASTM G 71 and G 82. Specific test standards for atmospheric galvanic corrosion can be found in ASTM G 116 and G 149, and ISO 744l, as described above.

Computer Modeling
Interpretation of results from computer models is straightforward, since the results are usually potential maps that can be related back to current density maps by using the polarization curves of the appropriate materials, or the current density maps, themselves. Faraday's Law can be applied to the current densities to determine the corrosion rates over the various surfaces. The results of this type of analysis always look good intuitively, with the potential 3ASTM G 1, Practice for Preparing, Cleaning, and Evaluating Corrosion Test Specimens; G 46, Practice for Examination and Evaluation of Pitting Corrosion.

ADDITIONAL INFORMATION
Additional information and details of galvanic corrosion testing are available in the standards referred to above and in Refs I0 and I1. Additional information on the theory of galvanic corrosion is available in Refs 12 to 22. A good series of articles summarizing galvanic corrosion theory and application in various industries is available in Ref 23. Galvanic corrosion testing descriptions are written at the level of a corrosion technician in Ref 11.

CHAPTER 20---GALVANIC 243

REFERENCES
[1] Tafel, J., Zeitschrift fur Elektrochemie und Angewandte Physikalische Chemie, Vol. 50, 1905, p. 641. [2] Hack, H. P., "Scale Modeling for Corrosion Studies," Corrosion, Vol. 45, No. 7, July 1989, pp. 601-606. [3] Tighe-Ford, D. J., McGrath, J. N., and Hodgkiss, L., "Design Improvements for a Ship's Cathodic Protection System Using Dimension and Conductivity Scaling (DACS)," Corrosion Prevention and Control, Vol. 32, No. 5, October 1985, pp. 89-91. [4] DeCarlo, E., "Computer Techniques for Offshore Corrosion Protection," Sea Technology, September 1981. [5] Clerbois, L., Heintz, E., IJselling, F., et al., "Principles for Scaling of Corrosion Tests," British Corrosion Journal, Vol. 20, No. 3, 1985, pp. 107-116. [6] Scully, J. R., "Electrochemical Methods of Corrosion Testing," Metals Handbook, Vol. 13, Corrosion, ASM, Metals Park, OH, 1987, pp. 212-216. [7] Baboian, R., "Prediction of Galvanic Corrosion Using Electrochemical Techniques," Electrochemical Techniques for Corrosion Engineering, R. Baboian, Ed., NACE, Houston, TX, 1986, pp. 253-258. [8] Baboian, R., "Final Report on the ASTM Study: Atmospheric Galvanic Corrosion of Magnesium Coupled to Other Metals," Atmospheric Factors Affecting the Corrosion of Engineering Metals, ASTM STP 646, S. Coburn, Ed., 1978, ASTM International, West Conshohocken, PA, pp. 17-29. [9] Blum, W., Symposium on Properties, Tests and Performance of Electrodeposited Metallic Coatings, ASTM STP 197, 1956, ASTM International, West Conshohocken, PA, p. 49. [10] Hack, H. P., "Evaluation of Galvanic Corrosion," Metals Handbook, Vol. 13, Corrosion, ASM, Metals Park, OH, 1987, pp. 234-238. [11] Hack, H. P., "Corrosion Testing Made Easy," Galvanic Corrosion, NACE International, Houston, TX, 1993. [12] Rowe, L. C. and Chance, R. L., "Fundamentals of Corrosion Testing," Automotive Corrosion by Deicing Salts, R. Baboian, Ed., pp. 142-146.

[13] Uhlig, H. H., Corrosion and Corrosion Control, John Wiley and Sons, New York, 1985. [14] Fontana, M. G., Corrosion Engineering, McGraw-Hill, New York, 1986, Chapters 9-10. [15] Shoesmith, D. W., "Kinetics of Aqueous Corrosion," Metals Handbook, Vol. 13, Corrosion, ASM, Metals Park, OH, 1987, pp. 29-36. [16] Baboian, R., "Electrochemical Techniques for Predicting Galvanic Corrosion," Galvanic and Pitting Corrosion--Field and Laboratory Studies, ASTM STP 576, R. Baboian, W. France, Jr., L. Rowe, and J. Rynewicz, Eds., ASTM International, West Conshohocken, PA, 1976, pp. 5-19. [17] Baboian, R., "New Methods for Controlling Galvanic Corrosion," Machine Design, Vol. 11, October 1979, pp. 2-9. [18] Tomashov, N. D., Theory of Corrosion and Protection of Metals, MacMillan Company, New York, 1966. [19] Baboian, R., "Investigations of Galvanically Induced Localized Corrosion," Localized Corrosion--Cause of Metal Failure, ASTM STP 516, ASTM International, West Conshohocken, PA, 1972, pp. 145-163. [20] Compton, K. G., "Current Density Distribution on Composite Structures under Cathodic Protection in Seawater," Galvanic and Pitting Corrosion Field and Laboratory Studies, ASTM STP 576, R. Baboian, W. France, Jr., L. Rowe, and J. Rynewicz, Eds., ASTM International, West Conshohocken, PA, 1976, pp. 48-55. [21] Hack, H. P., Moran, P. J., and Scully, J. R., "Influence of Electrolyte Resistance on Electrochemical Measurements and Procedures to Minimize or Compensate for Resistance Errors," The Measurement and Correction of Electrolyte Resistance in Electrochemical Tests, ASTM STP 1056, L. L. Scribner and S. R. Taylor, Eds., ASTM International, West Conshohocken, PA, pp. 1-16. [22] LaQue, F. L., Marine Corrosion, Causes and Prevention, John Wiley and Sons, New York, 1975. [23] Galvanic Corrosion, ASTM STP 978, H. P. Hack, Ed., ASTM International, West Conshohocken, PA, 1988.