Iron-chromium-nickel alloys pitting corrosion

Among the alloying elements used to improve the corrosion resistance of passivated alloys, molybdenum plays a central role in stainless steels. Indeed, stainless steels (iron-chromium or iron-chromium-nickel alloys) that contain molybdenum offer much better corrosion resistance (especially against pitting) than those without molybdenum. Despite the enormous amount of research work carried out on the process involved, using surface analytical methods combined with electrochemical measurements, the exact mechanism of the effect of molybdenum is not fully understood, and is still a matter of debate. However, all the data indicate that the improved corrosion resistance brought about by alloyed molybdenum is due to different phenomena, which may be rationalized in the following way ... 

The major alloying element contributing to resistance to pitting corrosion in iron- and nickel-base alloys is chromium. The effect of chromium in reducing both the critical current density and the passivating potential of iron in 1 N H2S04 is shown by the polarization curves of... 

By alloying nickel with both molybdenum and chromium, an alloy is obtained resistant to oxidizing media imparted by alloyed chromium, as well as to reducing media imparted by molybdenum. One such alloy, which also contains a few percent iron and tungsten (AUoy C), is immune to pitting and crevice corrosion in seawater (10-year exposure) and does not tarnish appreciably when exposed to marine atmospheres. Alloys of this kind, however, despite improved resistance to Cl, corrode more rapidly in hydrochloric acid than do the nickel-molybdenum alloys that do not contain chromium. 

Description and corrosion resistance. Incoloy 825 is a nickel-iron-chromium alloy with additions of molybdenum and copper. It has excellent resistance to both reducing and oxidizing acids, stress-corrosion cracking, and localized attack such as pitting and crevice corrosion. The alloy is especially resistant to sulfuric and phosphoric acids. 

Water environments can also have a variety of compositions and corrosion characteristics. Freshwater normally contains dissolved oxygen as well as minerals, several of which account for hardness. Seawater contains approximately 3.5% salt (predominantly sodium chloride), as well as some minerals and organic matter. Seawater is generally more corrosive than freshwater, frequently producing pitting and crevice corrosion. Cast iron, steel, aluminum, copper, brass, and some stainless steels are generally suitable for freshwater use, whereas titanium, brass, some bronzes, copper-nickel alloys, and nickel-chromium-molybdenum alloys are highly corrosion resistant in seawater. 

The properties of the interface metal/solution. Cast iron corrodes because of exposure of its graphite to the surface (graphitic corrosion), which is cathodic to both low-alloy and mild steels. The trim of a valve must always maintain dimensional accuracy and be free of pitting and hence it should stay cathodic to the valve body. Hence, in aggressive media, valve bodies are frequently chosen of steel rather than cast iron. Because of increased anodic polarization, low-alloy steel (Cr and Ni as noble components) is cathodic to normal steel in most natural media. Accordingly, steel bolts and nuts coupled to underground mild steel pipes, or a weld rod used for steel plates on the hull of a ship, should always be of a low-nickel, low chromium steel or from a similar composition to that of the steel pipe.7... 

Alloys such as 304 and 316 stainless steel or nickel-chromium cdloys exhibit deep pitting in low flow conditions, yet at high seawater velocities their corrosion rate decreases to less than 25 pm per year. Contrary to this, iron and copper show significantly lower corrosion rates at low flow velocities than rmder high seawater flow conditions [37]. 

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