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September 17, 2007
Volume 85, Number 38
p. 20

Rust Never Sleeps

Foiling Corrosion Involves Outsmarting Metals' Nature

Alexander H. Tullo

As soon as we are old enough to leave a bicycle out in the rain, we become familiar with the process of rusting. But metal rusting, or corrosion, is more than just a nuisance responsible for a couple of squeaky wheels. Corrosion costs the U.S. economy $276 billion per year, according to a 2002 report by the Federal Highway Administration.

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Pierre Roberge is a professor of chemistry and chemical engineering at the Royal Military College of Canada in Kingston, Ontario. An expert on rust, he has taught courses on the subject, written books, and served as a consultant. Corrosion, he points out, is inevitable if not prevented. "There are only a few metals that will be stable in our water-based environment," he says, noting that other metals, given the opportunity, will revert to mineral, orelike forms. "Most metals are found as oxides and sulfides. This is the way that the atoms arrange themselves in a stable form."

Iron, used to make steel alloys, is more stable as an oxide than as a metal. In the corrosion process, Roberge explains, iron oxidizes in the presence of water, yielding Fe2+ ions. The Fe2+ ions, meanwhile, react with hydroxide ions in the water to make Fe(OH)2, or "green rust," which reacts with oxygen in air to form Fe(OH)3—what we commonly recognize as rust.

It doesn't take a lot of water to begin the corrosion process, Roberge says. Even a moderate level of humidity will cause enough water to condense on a metal to initiate rusting. "It could just be a few molecules on the surface," he says.

We generally think of salt as a factor in rusting. It is, Roberge explains, but indirectly. The sodium and chloride ions in salt water add conductivity that accelerates the reaction of the iron. "It is a little like a battery," he says. "If you don't connect the battery, you stop the reaction."

Acidity will also accelerate rusting. Moreover, the corrosion process itself acidifies water, a problem that influences rusting in steel crevasses or joints and can lead to serious structural problems. Rust expands when it forms, Roberge points out, much as water does when it freezes. "Pack rust" can build immense pressure if left unchecked. "We have seen rivets popping out of very thick plates," he says. The phenomenon can also occur on aluminum structures such as airplanes.

Corrosion can be prevented or at least controlled. On steel structures such as bridges, paint provides a physical barrier between the moisture of the environment and the metal substrate. But Roberge says there are usually some defects and failures in the coating system.

That's why those charged with maintaining such structures tend to use primer coatings rich in zinc. Zinc is a metal lower in the galvanic series than steel, meaning it is more active and has a greater tendency to corrode. Thus, when exposed to the elements, zinc will corrode before the steel does. The same principle is at work in galvanization, whereby steel is plated with zinc.

Stainless steel is a more costly alloy of iron and other metals, most important among them chromium, which forms a stable oxide that halts the corrosion process, Roberge says. This is similar, he notes, to anodization of aluminum, in which a stable oxide layer is formed on the surface to prevent further corrosion. For ordinary steel, there is no such luck; rust is porous and water can always penetrate down to the nonrusted surface. "It will go right through the steel if you give it a chance," he says.

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Chemical & Engineering News
ISSN 0009-2347
Copyright © 2011 American Chemical Society

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