Iron-molybdenum alloys, pitting

Because the binary nickel-molybdenum alloys have poor physical properties (low ductility, poor workability), other elements, for example, iron, are added to form ternary or multicomponent alloys. These are also difficult to work, but they mark an improvement over the binary alloys. Resistance of such alloys to hydrochloric and sulfuric acids is better than that of nickel, but it is not improved with respect to oxidizing media (e.g., HNO3). Since the Ni-Mo-Fe alloys have active corrosion potentials and do not, therefore, establish passive-active cells, they do not pit in the strong acid media to which they are usually exposed in practice. 

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. 

Replacing some of the nickel with iron produces a family of alltws with intermediate corrosion resistance between stainless steels and the Ni-Cr-Mo alloys. Alloys such as Incoloy 825 and Hastelloy G-3 and G-30 are in this family. Incoloy 825 has 40 percent Ni, 21 percent Cr, 3 percent Mo, and 2.25 percent Cu. Hastelloy G-3 contains 44 percent Ni, 22 percent Cr, 6.5 percent Mo, and 0.05 percent C maximum. These alloys have extensive applications in sulfuric acid systems. Because of their increased nickel and molybdenum contents they are more tolerant of chloride-ion contamination than are standard stainless steels. The nickel content decreases the risk of stress-corrosion cracking molybdenum improves resistance to crevice corrosion and pitting. Many of the nickel-based alloys are proprietary and are coverecf by the following specifications ... 

Incoloy 825 (UNS N08825) has a substantially higher iron content and lower nickel content when compared to Inconel 625. Incoloy 825 also contains lower molybdenum content when compared to Inconel 625. Titanium (around 1% by weight) is added to Incoloy 825. The aUoy has sufficient resistance to CSCC and pitting. The alloy, however, has significantly lower strength compared to Inconel 625. 

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 ... 

Indeed, numerous experimental studies have been performed to study the evolution of the enviromnent in a crevice. Most data were obtained in actively corroding artificial crevices or pits, either by sampling the solution or by direct pH and Cr concentration measurements. Table 1 summarizes significant results that confirm the foregoing trends. In crevice solutions, the drop of pH depends on the hydrolysis constants of the metal cations. On stainless alloys, chromium and molybdenum are considered to be the cause of the very low, sometimes negative, pH observed. Iron, nickel, and aluminiun exhibit much less acidic hydrolysis reactions and the pH values in the crevices are higher values of 3 to 5 are reported for iron, values of 3 to 4 for the aluminum alloys. 

---