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GALVANIC / DISSIMILAR METAL CORROSION

WHAT IS GALVANIC CORROSION? Galvanic corrosion is a localized corrosive attack that may occur, if two dissimilar metals are in physical contact and exposed to the same corrosive environment. Oxidation (corrosion) increases on the less noble metal (anode) and reduction (normally oxygen reduction) occurs on the more noble metal (cathode) compared to the situation in which the metals are exposed to the same corrosive environment without physical contact. Oxidation (corrosion) Metal Metal+ + eReduction O2 + 2H2O + 4e4(OH-) (Neutral solutions, from fresh water to sea water) The nobility or the tendency of a metal to be affected by galvanic corrosion, when coupled with a dissimilar metal, can be ranked by comparison of the corrosion potentials of the two metals in the service environment. One such electrochemical potential series or galvanic series in seawater is given in Figure 1, which indicates that the "anodic" or "less noble" metals at the negative end of the series, such as magnesium and zinc, are more likely to be attacked than the "cathodic" or "more noble" metals at the positive end of the series, such as graphite and platinum. WHAT CONDITIONS ARE NEEDED? For galvanic corrosion to occur three conditions must be met: There must be metal to metal contact; The metal joint must be wetted with a conductive liquid (electrolyte); The metals potentials. must have sufficiently different

FACT SHEET #10

Prepared by Geir Moe, June 2010

2) The metal junction must be wetted by a conductive liquid (electrolyte) The conductivity of the liquid has a direct relationship to the degree of corrosion. If the conductivity of the liquid is high (a common example is sea water) the galvanic corrosion of the less noble metal will be spread over a larger area. In low conductivity liquids the corrosion will be localized to the part of the less noble metal near the junction. Salt or industrial pollution increases the conductivity of water so galvanic effects are normally more severe near the coast or in heavy industrial areas, thus rain water or condensation may become sufficiently conducting after contact with common environmental contaminants. Low conductivity liquids such as pure rainwater will only cause slight galvanic effects. One complication is that during evaporation, water films become more conductive as the liquid becomes more concentrated. NOTE: Galvanic attack can be prevented by ensuring that no electrolyte remains at the dissimilar metal junction. This may require extra attention to drainage or to protection from the electrolyte. A good covering of paint or sealant, 30 to 50 mm beyond the joint, may prevent ion transport in any thin water film. 3) Metals must be far apart on the galvanic series The critical point is the difference in potential of the two dissimilar metals. A difference of hundreds of millivolts is likely to result in galvanic corrosion, but only a few tens of millivolts are unlikely to be a problem. NOTE: Figure 1 shows there are two different potentials associated with each stainless steel grade. The usual, passive behaviour is shown by the lightly bordered box. However, if the passive film breaks down, which might occur in a crevice, the stainless steel corrodes and its potential is in the dark bar range. Passive Surface Films Stainless steels naturally form corrosion resistant passive surface films. This film also reduces the amount of current available for corrosion; thus slows the corrosion rate compared to some other galvanic pairs. For example, if the behaviour of a copper/mild steel couple and a 316L/mild steel couple is compared, the copper/mild steel couple is a more significant galvanic problem despite the greater potential difference between 316L and mild steel.

1) The metals must be in electrical contact The dissimilar metals must be in electrical contact with each other. The metals can be bolted, welded or clamped together, or even just resting against each other, or bridged by an intermediary conductive material. If the dissimilar metals are insulated from each other by suitable nonconductive strips, washers or sleeves, then galvanic corrosion cannot occur. NOTE: Paint is not a reliable electrical insulator since it may be easily damaged during installation or by subsequent movement. Only painting the less noble metal, such as carbon steel, can cause aggressive attack where the paint is damaged because corrosion will be concentrated at these locations.

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THE AREA EFFECT The relative area of the anode (less noble) metal and the cathode (more noble) metal has a pronounced effect upon the amount of corrosion that occurs. A small anode area joined to a large cathode area will result in a high current density on the anode (less noble) metal, and hence a high rate of corrosion. This area effect was seen as early as the 1760s, on a wooden hull British naval frigate that was sheathed in copper to prevent attack by barnacles. It was soon discovered that the copper sheathing (more noble metal) had become detached from the hull in many places because the iron nails (less noble metal), which had been used to fasten the copper to the timbers, had been quickly corroded. Some nails, which were less corroded, were insulated from the copper by brown paper which was trapped under the nail head. The copper had been delivered to the dockyard wrapped in the paper, which was not removed before the sheets were nailed to the hull. Not only is sea water a very good electrolyte owing to its high salt concentration, but attack of the nails was encouraged by their very small exposed area compared with that of the copper sheets. Conversely if the anode area is large compared to that of the cathode this distributes the corrosive attack over a larger area reducing the severity of the attack. As a rule of thumb, if the wetted area of the anode (corroding metal) is 10 times the wetted area of the cathode (noble metal), then galvanic effects are not serious; obviously, increasing the ratio of anode to cathode area will reduce the attack even further. An apparent contradiction of the area effect occurs when the two metals are only partially wetted. Consider for instance a stainless steel bolt in an aluminum plate; if water (electrolyte) collects under the head of the bolt, but the remainder of the aluminum plate remains dry, the area of the less noble aluminum that will suffer galvanic attack is only the wetted region under the head of the bolt. Only the wetted area counts. NOTE Galvanic corrosion, to be operative, requires one of the metals in the galvanic couple to be corroding. Thus galvanic corrosion is rarely seen on alloys that are resistant to the service environment.

FACT SHEET #10

The intensity of galvanic corrosion is determined by several factors: a) electrolyte conductivity; b) localized changes in electrolyte concentration; c) the size of the potential difference between the dissimilar metals; oxygen content; the presence of passive surface films; shielding of metal surfaces, by deposits or surface coatings.

d) the anode-to-cathode area ratio; e) f) g)

Thus it can be difficult to precisely predict the potential for galvanic corrosion. Galvanic attack of the anode is spread over a large area when exposed to a high conductivity electrolyte, such as brackish water or sea water; but, is confined to the immediate area of the dissimilar metal junction in fresh water, which is a low conductivity liquid. Galvanic attack is often negligible in deaerated electrolytes because in neutral pH solutions, oxygen is necessary for the reduction reaction at the cathode, which consumes the electrons released during the corrosion of the less noble metal (anode). Reduction (cathode) O2 + 2H2O + 4e4(OH-)

However, when oxygen is absent or significantly reduced, corrosion is either eliminated or greatly reduced. In neutral electrolytes galvanic attack of the anode can be significantly reduced by coating the cathode, which reduces the area available for the ratecontrolling oxygen reduction reaction. Removal of coatings from the anode may also be beneficial by distributing any galvanic attack over a larger area. Galvanic corrosion can occur between difference constituents of the same metal, such as iron embedded in the surface of stainless steel or sulphide inclusions in re-sulphurized stainless steels, such as 303 (UNS S30300).

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CONTACTS Ted Barrette, P.Eng. Supervising Mechanical Engineer 905 469 3403 ext 7334 ebarrette@hatch.ca Geir Moe, P.Eng. Senior Materials Engineer 905 469 3403 ext. 7355 gmoe@hatch.ca Victor Taylor Senior Welding Technologist 905 469 3403 ext. 7312 vtaylor@hatch.ca

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FACT SHEET #10

Figure 1: Galvanic Series of Various Metals in Flowing Seawater at 2.4 to 4.0 m/s for 5 to 15 Days at 5 to 30oC (ASTM G82)
(Redrawn from original LaQue, F. L., Marine Corrosion, Causes and Prevention, John Wiley and Sons, New York, NY, 1975) NOTE: Dark boxes indicate active behaviour of active-passive alloys