Marine Metal Corrosion, by D.

Wesley Fowler Page 1 of 1

Marine Metal Corrosion

A Layman's Guide to Corrosion Associated With Pleasure Craft Metals D. Wesley Fowler, S.A. One of Mother Earths dichotomies is her seasthey are so beautiful, yet so destructive. If you've ever owned a sizeable boat you know what it means having to pile money into an endless maintenance budget, largely to prevent the many different kinds of damage that seawater can bring. "A boat is a hole in the water into which you pour money." Day in and day out, vessel owners have to spend money and time having shipyards install preventive measures to avert or hinder damage to a hull and underwater machinery so that it can stay in good condition from remaining in seawater for long periods. One of the most common and costly types of damage is corrosion. When most people hear the word corrosion they think of rust, the reddishcolored oxide product of iron or steel. In the marine transportation industry, for material costs sake, some large vessels are made of carbon steel i.e. ships, barges, tugs, etc. In order to protect these vessels from corrosion their hulls are covered with layers of specialized paints, industrial-sized sacrificial anodes are bolted to their hulls, and/or they may be alternately protected by way of an automatic impressed current cathodic protection system. But as pleasure craft owners most of the types of metals that we find on our vessels are usually of higher quality, such as Austenitic stainless steels, different series of aluminum, bronzes of different alloys, and monel. What is surprising is that there are many experienced mariners and even some manufacturers who believe that these types of metals will not corrode. This is untrue and unfortunately this mistaken belief has proven to be very costly. Galvanic Corrosion Before delving into how specific types of marine alloys corrode, the basic physical mechanism by which most marine corrosion takes place should be understood. "Galvanic" corrosion occurs when two different types of metals are put into physical contact with each other while they are immersed in an electrolyte, such as seawater. The reason corrosion takes place between two different, coupled metals is that a voltage difference (potential) exists between them. For example, many midsized sailboat propulsion shafts are made of 300 series stainless steel, which possesses an average voltage of -0.07V. These sailboat shafts are frequently connected to bronze propellers, which possess an average voltage -0.26V. The voltage difference between these two coupled metals is approximately .19V. Since

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bronze possesses the lower voltage of the two metals it is more anodic, therefore it is the active metal, and as such will begin to corrode over time. For further illustration refer to the Galvanic Series chart below. First, note that most of the different types of metals listed on the chart are of the kinds that are used in the marine industry for one purpose or another. You should also see that these metals are arranged from greatest to least in their voltage values. Lastly, it is important to recognize that the metals which possess the lower voltage values are located at the anodic or "active" end of the scale and the metals which possess higher voltage values ascend to the cathodic or "passive" end of the scale.

GALVANIC SERIES
in moving seawater

Cathodic or "Passive" End

Alloy

Voltage Range of Alloy vs. Reference Electrode

Graphite +0.30 to +0.20 Platinum +0.25 to +0.18 Hastelloy C-276 +0.10 to -0.04 Inconel 625 +0.10 to -0.04 Titanium +0.06 to -0.05 300 Series Stainless Steel 0.00 to -0.15 Monel -0.04 to -0.14 Silver -0.09 to -0.14 70-30 Copper-Nickel -0.13 to -0.22 Lead -0.19 to -0.25 90-10 Copper-Nickel -0.21 to -0.28 Silicon Bronze -0.24 to -0.27 Manganese Bronze -0.25 to -0.33 Admiralty Brass -0.25 to -0.34 Copper -0.28 to -0.36 Red Brass, Yellow Brass, Naval -0.30 to -0.40 Brass Aluminum Bronze -0.30 to -0.40 Steel -0.60 to -0.70 Cast Irons -0.60 to -0.72 Cadmium -0.70 to -0.76 Aluminum Alloys -0.70 to -0.90 Zinc -0.98 to -1.03 Magnesium -1.60 to -1.63 Anodic or "Active" End

There are two factors (among many others variables) that constitute the rate at which galvanic corrosion takes place, one being the total voltage difference between two coupled metals, and the other being the size of the cathodic metal in relation to

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the anodic metal. In other words, larger voltage differences stimulate more rapid corrosion; and, the larger the physical size of the cathodic metal in comparison to the anodic metal, the more rapid the rate of corrosion. Without probing too deeply into the reason why and how ions are exchanged during the corrosion process, it could be quickly summed up by explaining that the anode (negative pole) possesses more electrons than the cathode (positive pole). Corrosion is facilitated by these electrons flowing from negative to positive. In order to minimize galvanic corrosion, if it is not practical to install materials that are non-metal or non-absorbent between the dissimilar metals to prevent electrical current flow, then both of the metals can be painted to reduce the area of the exposed metal surfaces. But the most successful method in protecting both metals is to connect both of them to a third metal that is more anodic than the original coupled metals. In this case, the third metal becomes a sacrificial anode and the two original metals will remain passive. This is a common way that is used to inhibit corrosion on the submerged portions of marine vessels. Note that the sacrificial anode should never be painted. By understanding the basics of how galvanic corrosion occurs it will be easier to grasp the different ways that marine metals can corrode. Stainless Steel Stainless steel is one of the most misunderstood metals in the boating industry. Since corrosion on stainless steel is not readily or visibly apparent, as is the case with carbon steel, many assume that stainless will not corrode. It is true that some types of stainless steel are resistant to corrosion, however when stainless is exposed to certain conditions it will corrode, only not in the manner one would normally expect to see. To explain, in order for stainless steel to remain in a passive (non-corrosive) state the chromium portion of the metal must be provided with oxygen to form a protective oxide layer. Our atmosphere normally provides a sufficient amount of oxygen to the stainless steel to maintain this passive oxide layer, which is why it is generally acceptable for use above the waterline on a boat if it is installed properly. But when stainless is submerged it may not receive the oxygen that is required for it to remain passive, which is why using stainless steel below the waterline without some form of protection against corrosion is not a great idea. Following are some different examples of how stainless steel can corrode. Pitting Corrosion Pitting is one of the types of corrosion that can occur on stainless steel, along with some other types of marine metals, and as previously stated it is generally caused when the metals protective oxide layer is compromised, as could be the case if it was submerged with no anodic protection. Even in the worst cases, almost all of the metals surface will remain protected, yet small, local inconsistencies in its protective oxide layer will exist at certain points along the surface. The reduction in oxide protection at certain points along the metal's surface causes these areas to

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become anodic, or active. At the same time, the areas surrounding the active parts of the metal surface that still contain sufficient oxide protection act cathodic, and remain passive. Seawater, being an electrolyte, provides the path for the ions of the anodic areas to transfer to the surrounding cathodic areas of the metal. This localized, galvanic attack continues over a period of time until a pit, or many pits form, while the surrounding metal remains virtually corrosion free. Meanwhile, the water inside the cavity-like pits becomes mildly acidic due to the increased concentration of hydrogen and chloride ions, which causes the rate of corrosion to become more aggressive. These pit sizes can range from pinholes to large, shallow depressions. Here is a drawing to help depict how pits form. Crevice Corrosion Similar to pitting, crevice corrosion also occurs from a lack of oxygen concentration on the surface of stainless steel, especially in areas along the metal surfaces that may contain a sharp or right-angle bend. This type of corrosion may occur at areas where fasteners pass through holes, or where washers or gaskets are fastened against a stainless steel surface, or in corners where two metal surfaces join or are in close proximity to each other. It can even develop at locations where dirt or grime covers the metals surface. In essence, it can occur anywhere there is a possibility that oxygen is depleted--in stagnant water, or where there exists a nook, cranny, or crevice. Stress Corrosion Cracking Stress corrosion cracking (SCC) is an insidious type of corrosion that can occur when stainless steel develops very minute cracks from being under tensile stress. Most sailors know that a sailboats standing rigging is one of the areas on the vessel that bears considerable load. The components on the rigging that are stressed while the vessel is under sail include the chainplates, stempiece, and their bolting systems; backstay connections to the stern; toggles and clevis pins; rolled swages; tangs (shroud connections to the mast); the actual stays and shrouds, etc. One component of a sailing vessels standing rigging that is particularly vulnerable to SCC are stainless steel chainplates which pass through cored decks. (Click here to view photo presentation of damage survey performed on dismasted Pearson 303.) In this case, part of the chainplate passes through the deck and is permanently embedded in the cored space. This is the point at which the chainplate is deprived of a normal amount of fresh oxygen. It is not uncommon to find that some of these chainplates are fully sealed with compound around the area where they penetrate the deck. After long-term exposure to weather sometimes the compound will crack which will then provide a path for rain or seawater to enter and become trapped in the cored area. This is how the electrolyte is introduced, creating a situation that could support galvanic activity. Enter tensile stress into this equation. As mentioned before, while a vessel is under sail several components of the rig are under a considerable load, particularly the windward chainplate. Over time, this dynamic stress load can cause tiny cracks

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to be created at different points along the chainplate. With trapped, stagnant water present and no protective oxide layer provided, and also with the chainplate containing cracks from previously being stressed, all of the ingredients are present for SCC to take place. Allowed to galvanically fester over a period of time, one day an unsuspecting owner takes his or her boat for a sail. While sailing with a normal stress load on the rig, the chainplate suddenly fractures and the boat is dismasted--the "surprise" beginning of a very bad day on the water. Characteristically, SCC may show tiny, crazed type, brittle-appearing cracks at certain stressed places along the surface, while the rest of the stainless may appear free of any defects. Dont let these elusive, harmless-looking cracks fool you because they usually propagate throughout the metal. Metals that have suffered from SCC, when exposed to normal design tensile stresses, may fracture well below normal yield strengths. The types of chainplates used in the example above are problematic when it comes to inspecting them because of how they are installed. In order for all of the vulnerable areas to be inspected for SCC the chainplates have to be removed to reveal the area that is normally hidden in the cored deck so that they can be closely examined, along with fastener holes, fasteners, and other areas which bear tensile stress along the plate. Obviously, removing a chainplate is a procedure that should be carefully planned to avoid a possible rigging mishap, which could result in serious injury or death. If you are not experienced in performing this kind of task you should consider consulting or contracting a qualified or competent rigging specialist. Brass and Bronze Brasses and bronzes are yet another misunderstood group of metals that are used in the marine industry. The similarity between bronze and brass is that they are both primarily comprised of copper; however, the percentage of copper and the types of alloying elements are what also differentiate them from one another. Generally, bronzes are alloys that are comprised of 90% copper (or more) along with tin, aluminum, or silicon, and in some cases trace percentages of other elements. Conversely, the copper content of most brass alloys can generally range anywhere from about 45% to 70%, along with a large percentage of zinc, and perhaps trace amounts of other elements. "Dezincification" Of these two types of copper-based metals the one that is most susceptible to corrosion is brass, chiefly due to its zinc content. Any type of brass part that contains zinc of at least 16% or greater is subject to a type of corrosion called "dezincification". Dezincification is when the zinc portion of the brass alloy is carried away from the mother metal as a soluble salt. The dezincification of brass can take place when brass is used near a sea water environment, and the corrosion extent and rate will increase if it is submerged.

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One indication that this form of corrosion is taking place on any brass part is that the part will appear to be more of a reddish, copper color versus its normal, brassyyellow tone. Any nuts, bolts, and/or other hardware installed above the waterline can flake or scale away at a rate of about .003" of brass per year if the corrosion is allowed to progress. More severely, if any brass part is used below the waterline it is more likely to pit. The initial pit may be small in size but will grow at an alarming rate--as much as one eighth of an inch per year, which can clearly cause the brass part to disintegrate more quickly. These are reasons why it is not advisable to use brass for seacocks, through-hull fittings, or structural applications/fittings on the boat. The correct metal between brass and bronze for seacocks, through-hulls, or other structural applications is bronze. On boats, brass should probably be restricted to use for decorative purposes, as most alloys of brass do shine well when they are polished. Copper Unalloyed copper, by itself, will form a protective oxide layer, such as the green patina seen on copper steeples, when exposed to the atmosphere which makes it naturally resistant to corrosion. However, if it is immersed and exposed to moving seawater, its rate of corrosion increases proportionately to the velocity of the moving seawater. In the early stages of this type of copper corrosion the seawater motion initially removes the protective oxide film layer, which creates a condition that stimulates the metal to corrode. If allowed to continue the copper could suffer impingement damage or "erosion corrosion", where the moving seawater continues to remove the oxide layer, further stimulating corrosion, but at the same time mechanically removing the corrosion product from the metal surface. Copper is also a very weak metal without zinc or other metals to improve its strength. Cupronickel is a mixture of nickel and copper (10% nickel to 90% copper) which is highly resistant to corrosion from moving seawater, so it can be used in moving salt water applications. Aluminum Aluminum is the most used metal in the pleasure craft industry, primarily because of its high strength to weight ratio, abundance, and relatively low cost. It is used in a variety of applications: masts, booms, some engine blocks, tanks, "T-tops" and railing, some running-rigging blocks, etc. There are many "series" of aluminum, all of which vary in their alloying content, but in marine applications usually series 5000 or 6000 is used, mainly because both are comprised of some mix of aluminum/magnesium or aluminum/magnesium/silicon. Aluminum possesses a high resistance to corrosion, again, which is primarily due to a thin film of aluminum oxide that forms on the surface when it exposed to the atmosphere. The oxide layer usually turns gray and becomes dull looking after some exposure. Aluminum's resistance to corrode is resilient, for even if it is scratched or gouged the protective surface oxide layer will return.

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Usually, aluminum will pit if it is exposed over the long term to air and salt or fresh water. It can also crevice or stress corrode (as explained in paragraphs before) but the real problem with aluminum corrosion arises when it is placed in contact with another more noble metal while in the presence of an electrolyte. Because of where aluminum ranks on the Galvanic Scale (see page 2), it will likely be the anodic metal if it is coupled with another metal. An example of this can be seen regularly on aluminum masts or booms that have had low-grade stainless steel fasteners installed in them for cleats or other rigging attachments. Usually a small area of corrosion will form where these fasteners penetrate the mast or boom aluminum sections. This is best eliminated by using fasteners that are comprised of monel or aluminum. There is a potentially dangerous situation that mariners should be particularly aware of concerning the corrosion of aluminum fuel tanks, especially when they are used in a gasoline system. Many tank manufacturers will, either through ignorance or neglect, install brass valves and fittings directly into the fuel tank without a noncorrosive barrier to separate the two metals. Galvanically, aluminum and brass react to each other very strongly, leading the tank to eventually corrode, thereby creating the very dangerous potential for fuel to leak. However, brass fittings can safely be used in these types of applications if they are separated from contact with the aluminum tank by use of a stainless steel insert. Aluminum tanks are also frequently installed incorrectly in some small boats by manufacturers that do not follow the Coast Guard Fuel System Standard or American Boat and Yacht Council recommendations for fuel tank installations. For the sake of saving space in these small fishing boats, manufacturers will install a tank below the weather deck, fill the space around the tank with insulation material, and then provide little, if any drainage avenues to remove water/moisture from the tank compartment. As previously stated, salt water will corrode aluminum, so it is important that all tanks be installed such that water cannot be entrapped against any tank surface and so that all surfaces can be drained quickly. There are some methods that are used in the manufacture of aluminum parts such as masts, booms, etc., that help stifle corrosion, such as anodizing. Aluminum can also be painted by using special paints, as long as they do not contain mercury, copper, or lead, as these can cause galvanic corrosion. Monel Monel is probably the best metal that can be chosen for use in the marine industry. This alloy ranks fairly high on the Galvanic Scale and is comprised of two-thirds nickel and one-third copper. It possesses high tensile strength (slightly less than 300 series stainless steels), is very ductile, and it is highly resistant to corrosion from atmospheric and sea water exposure. One of monel's best qualities is that it is most corrosion resistant in moving sea water. There are a variety of parts that are comprised of monel for marine use such as annular-threaded nails, screws, nuts,

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bolts, props, prop shafts, even wire rope. Monel can pit if it is exposed to long-term stagnant salt water, but very, very rarely. One indication that monel is beginning to corrode is when a grayish-green patina forms on the metal's surface. However, as stated before, it is a rare occasion to see corrosion develop on monel.

******************************************************************** This information was written and published so that the average mariner could gain a basic understanding of the different types of alloys that are generally used in marine applications and how they can corrode, which could further cause damage to or loss of vessels or personal injury to mariners and/or their guests. Although the metals in this publication were written of broadly, there are many variations of these alloys that were not specifically addressed. The use of each metal component in a vessel's structural application or in one of its on-board systems should be in accordance to manufacturer's specifications or by proven, accepted engineering practices. Always consult or contract a SAMS or NAMS marine surveyor, or a competent marine repair or rigging service before attempting to install or repair any system aboard your vessel in which you have no specific design or operational knowledge. ********************************************************************